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Journal articles on the topic 'H‐insertion reaction'

Author: Grafiati

Published: 4 June 2025

Last updated: 23 June 2025

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1

Calter, Michael A. "Transition Metal-Catalyzed, Asymmetric Reactions of Diazo Compounds." Current Organic Chemistry 1, no. 1 (1997): 37–70. http://dx.doi.org/10.2174/1385272801666220121184444.

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The past ten years have seen impressive advances in asymmetric synthesis. This review summarizes the recent advances in a particular set of asymmetric reactions, the reactions of diazo compounds catalyzed by transition metal complexes. Additionally, the emphasis of this summary is on reactions wherein the induction arises from a catalyst or an auxiliary, rather than some inherent asymmetry of the substrate. The covered reactions fall into two reaction types; cyclopropanations and insertions. The cyclopropanation section of this review describes how high stereoselectivities are possible using either chiral auxiliaries or various metal complexes. Both these strategies are effective for producing optically-enriched intermediates; however, the use of catalysts to control the stereochemistry of the cyclopropanation reaction is much more common than the corresponding use of auxiliaries Workers in the asymmetric cyclopropanation field have primarily used Cu(l) and Rh(ll) complexes as catalysts for these reactions, although several complexes of other metals do afford high asymmetric induction. Both inter- and intramolecular cyclopropanations afford synthetically useful selectivities. The insertion section of this review summarizes recent advances in the use of auxiliaries and catalysts for controlling the stereoselectivity of the insertion into various bonds. Insertion into C-H bonds are by far the most intensively studied, although there has been some success with asymmetric insertions into 0-H, S-H, Si-H and C-0 bonds. Complexes of Rh(ll) are almost universally employed for asymmetric insertions. As in the case of cyclopropanations, both inter- and intramolecular insertions can proceed with useful selectivities. Again, catalyst control has proven a more versatile way to control absolute stereochemistry than auxiliary control.

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2

YAN, BING-FEI, WEN-ZUO LI, YU-WEI PEI, QING-ZHONG LI, and JIAN-BO CHENG. "THEORETICAL INVESTIGATION ON THE INSERTION REACTIONS OF THE GERMYLENOIDH2GeLiFWITHRH(R=Cl,SH,PH2)." Journal of Theoretical and Computational Chemistry 12, no. 03 (2013): 1350003. http://dx.doi.org/10.1142/s021963361350003x.

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The insertion reactions of the germylenoid H2GeLiF with RH (R = Cl, SH , PH2) were studied for the first time by using the DFT B3LYP and QCISD methods. The geometries of the stationary points on the potential energy surfaces of the reactions were optimized at the B3LYP/6-311+G (d,p) level of theory. The calculated results indicated that the mechanisms of the insertion reactions of H2GeLiF with HCl , H2S , and PH3are identical to each other. The QCISD/6-311++G(d,p)//B3LYP/6-311+G(d,p) calculated potential energy barriers of the three reactions are 81.80, 123.39 and 205.56 kJ/mol, and the reaction energies for the three reactions are -58.74, -33.51 and -13.35 kJ/mol, respectively. Under the same situation, the insertion reactions should occur easily in the following order H–Cl > H–SH > H–PH2. The insertion reaction in THF solution is easier than in gas phase.

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3

Kakiuchi, Fumitoshi, Naoki Kimura, Shiori Katta, Yoichi Kitazawa, and Takuya Kochi. "Deuterium-Labeling Studies on the C–H/Olefin Coupling of Aromatic Ketones Catalyzed by Fe(PMe3)4." Synthesis 53, no. 18 (2021): 3383–89. http://dx.doi.org/10.1055/s-0040-1706040.

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AbstractDeuterium-labeling experiments were performed for the Fe(PMe3)4-catalyzed C–H/olefin coupling using a deuterium-labeled aromatic ketone with various alkenes. While the reactions with a variety of alkenes provided the linear alkylation products formed via 1,2-insertion of alkene into an Fe–H bond, the reversible 2,1-insertion proceeded during the reaction highly depends on the choice of the alkene. No H/D scrambling resulting from 2,1-insertion/β-elimination was detected for the reactions with a vinylsilane and N-vinylcarbazole, but the reactions with styrenes are considered to involve rapid 2,1-insertion/ β-elimination processes to cause significant levels of H/D scrambling.

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4

Wiberg, N., G. Preiner, G. Wagner, and H. Köpf. "Reaktivität des labilen, durch Adduktbildung mit Ph2C=NSiMe3 gespeicherten Silaethens Me2Si=C(SiMe3)2 / Reactivity of the Labile Silaethene Me2Si = C(SiMe3)2, Stored as Ph2C =NSiMe3 Adducts." Zeitschrift für Naturforschung B 42, no. 9 (1987): 1062–74. http://dx.doi.org/10.1515/znb-1987-0902.

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Silaethene Me2Si = C(SiMe3)2 (1), stored as Ph2C=NSiMe3 adducts and regenerated from the adducts at about 100 °C as a reaction intermediate, combines with reactants a-b (e. g. HO-H, RO-H. RCOO-H, RS-H. RHN-H, Ph2CN-H, RO-SiR3, R2N-SiR3, Ph2CN-SiR3, Cl-GeR3, Cl-SnR3) with insertion into the a-b bond, with a=b (e.g. 0 = CPh2, Me3SiN = CPh2, CH2=CHOMe, cis-piperylene), a=b=c (e.g. RN = N = N, O = N=N). a=b-c=d (e.g. butadiene, isoprene, trans-piperylene, 2,3-dimethylbutadiene, cyclopentadiene, anthracene, benzophenone, N-trimethylsilylbenzophenoneimine) under [2+2]-, [2+3]- as well as [2+A]-cycloaddition and with a=b-c-H (e.g. propene, butenes, isoprene. 2.3-dimethylbutadiene, acetone) under ene reaction. According to relative reaction rates, insertion and [2+2]-cycloadditions seem to proceed in two reaction steps, whereas [2+4]-cycloadditions and ene reactions with organic dienes and enes obviously are one step reactions. For relative reactivities cf. Table I.

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5

Khade, Rahul, Xinyi Zhao, Carolyn Wang, and Yong Zhang. "Biocatalytic Carbenoid N-H Insertions Via Engineered Myoglobins: A Systematic Reaction Mechanism Study." ECS Meeting Abstracts MA2024-01, no. 14 (2024): 1114. http://dx.doi.org/10.1149/ma2024-01141114mtgabs.

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Recently engineered myoglobins have demonstrated excellent biocatalytic activities for a broad range of carbenoid N-H insertion reactions with up to >99% yield. Such biocatalysts offer various tuning points beyond protein residues, such as metal center, and axial ligand, to regulate different chemical reactivities. However, there is no computational mechanistic study to reveal its basic reaction mechanism, which could be utilized to study effects of different catalyst component for rational biocatalyst design. The reported computational mechanistic papers of other heme protein catalyzed N-H insertion have limited information without a careful comparison of all possible pathways and just focused on certain steps. Building on our group’s recent mechanistic work on a number of heme carbene transfer reactions, we performed a quantum chemical study to systematically study all possible reaction pathways for myoglobin catalyzed N-H insertions, which starts from the reactants to final released products and thus constitute a complete reaction pathway study. We examined ylide (proton transfer), hydrogen atom transfer, and hydride transfer pathways. In the favored ylide pathways, we calculated the direct proton transfer from amine to carbene and indirect paths with both concerted and stepwise proton transfer and dissociation components. For the indirect pathways in which the proton resides on the carbonyl oxygen of the original carbene substituent, subsequent water-assisted proton transfer from this carbonyl oxygen to carbene’s carbon to form the final product was also investigated. The most favorable pathway from this systematic reaction mechanism study was further supported by new experimental work from our collaborators, the original developer of myoglobin-based biocatalysts. These novel mechanistic results provide important mechanistic information for future biocatalyst design with enhanced reactivities.

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6

Zhang, Xiaomei, Ming Ma, and Jianbo Wang. "Catalytic asymmetric S-H insertion reaction of carbenoids." Arkivoc 2003, no. 2 (2003): 84–91. http://dx.doi.org/10.3998/ark.5550190.0004.210.

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7

Li, Mao-Lin, Jin-Han Yu, Yi-Hao Li, Shou-Fei Zhu, and Qi-Lin Zhou. "Highly enantioselective carbene insertion into N–H bonds of aliphatic amines." Science 366, no. 6468 (2019): 990–94. http://dx.doi.org/10.1126/science.aaw9939.

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Aliphatic amines strongly coordinate, and therefore easily inhibit, the activity of transition-metal catalysts, posing a marked challenge to nitrogen-hydrogen (N–H) insertion reactions. Here, we report highly enantioselective carbene insertion into N–H bonds of aliphatic amines using two catalysts in tandem: an achiral copper complex and chiral amino-thiourea. Coordination by a homoscorpionate ligand protects the copper center that activates the carbene precursor. The chiral amino-thiourea catalyst then promotes enantioselective proton transfer to generate the stereocenter of the insertion product. This reaction couples a wide variety of diazo esters and amines to produce chiral α-alkyl α–amino acid derivatives.

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8

Cai, Yan, Haihong Ge, Weize Sun, and Zhiwei Miao. "Trifluoroborane-Catalyzed C–H Functionalization/S–H Insertion Reaction: Construction of N,S-Acetal Quaternary Centers." Synthesis 47, no. 11 (2015): 1669–77. http://dx.doi.org/10.1055/s-0034-1380384.

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The trifluoroborane-catalyzed C–H functionalization/S–H insertion reaction of α-diazophosphonates with thiols has been developed. A plausible reaction mechanism has been proposed to understand the combined reaction. This process provides straightforward access to N,S-acetals containing quaternary centers in moderate to good yields and chemoselectivity.

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9

Zhang, Ming-Xia, Ming-Jun Zhang, Wen-Zuo Li, Qing-Zhong Li, and Jian-Bo Cheng. "Structure ofH2GeFMgFand its insertion reactions withRH(R=F,OH,NH2)." Journal of Theoretical and Computational Chemistry 14, no. 01 (2015): 1550004. http://dx.doi.org/10.1142/s0219633615500042.

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The structures of the germylenoid H2GeFMgF and its insertion reactions with RH ( R = F , OH , NH2) were studied using the DFT B3LYP and QCISD approaches for the first time. The geometries of all of the stationary points were optimized at the B3LYP/6-311+G (d, p) level of theory. And then the QCISD/6-311++G (d, p) single-point energies were calculated. The solvent effects on the geometries and insertion reactions were also computed using the PCM model. The calculated results suggested that H2GeFMgF had three equilibrium configurations, in which the p-complex structure had the lowest energy and was the most stable structure. The isomerization reactions among the three complexes had been studied. For the insertion reactions of H2GeFMgF with RH ( R = F , OH , NH2), along the potential energy surface, there were one transition state and one intermediate which connected the reactants and the products. For the three insertion reactions the mechanisms are identical. However, under the same conditions the insertion reactions should occur easily in the order of H - F > H - OH > H - NH2. The solvent effect calculations suggested the larger the solvent polarity is, the easier the reaction will be.

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10

Chen, Lianfen, Chaoyi Zhao, Weixian Mo, Chunsheng Li, and Xiaoming Lin. "X-H Bond Insertion Promoted by Heterogeneous Dirhodium Metal–Organic Cage with Alkynes as Safe Carbene Precursors." Molecules 28, no. 2 (2023): 608. http://dx.doi.org/10.3390/molecules28020608.

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A facile and efficient methodology for the generation of the C-X (X = Si, B) bond through a carbene insertion process was demonstrated using a dirhodium metal–organic cage, MOC-Rh-1, as a heterogeneous catalyst. A series of functionalized alkynes were utilized as safe carbene precursors to furnish Si-H and B-H insertion products in moderate to excellent yields. These reactions featured a high atom-economy, a broad substrate scope, and mild reaction conditions. Moreover, the as-prepared MOC-Rh-1 catalyst was recovered easily from the reaction system by simple centrifugation and reused for ten runs without a significant loss in activity, which made good use of the valuable precious metal rhodium.

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11

Zhu, Shou-Fei, Qing-Qing Cheng, Ji-Min Yang, and Huan Xu. "Iron-Catalyzed Carbenoid Insertion into C(sp3)–H Bonds." Synlett 28, no. 11 (2017): 1327–30. http://dx.doi.org/10.1055/s-0036-1588743.

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An iron-catalyzed carbenoid insertion into C–H bonds of alkanes was developed with high activity (turnover numbers up to 690 in a gram-scale experiment) and chemoselectivity. This non-heme iron-catalyzed C(sp3)–H insertion reaction provides an efficient strategy for C–H functionalization.

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12

Gerbig, Dennis, David Ley, Hans Peter Reisenauer, and Peter R. Schreiner. "Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene." Beilstein Journal of Organic Chemistry 6 (November 11, 2010): 1061–69. http://dx.doi.org/10.3762/bjoc.6.121.

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The first C–H insertion of a hydroxycarbene species in the gas phase has been observed experimentally by means of high vacuum flash pyrolysis (HVFP) and subsequent matrix isolation: (o-Methoxyphenyl)glyoxylic acid gives non-isolable (o-methoxyphenyl)hydroxycarbene upon pyrolysis at 600 °C, which rapidly inserts into the methyl C–H bond. The insertion product, 2,3-dihydrobenzofuran-3-ol, was trapped in an excess of Ar at 11 K and characterized by infrared spectroscopy. The insertion process kinetically outruns the alternative [1,2]H-tunneling reaction to o-anisaldehyde, a type of reaction observed for other hydroxycarbenes. Traces of the dehydration product, benzo[b]furan, were also detected. The potential energy hypersurface including the insertion and hydrogen migration processes was computed at the all-electron coupled-cluster level of theory encompassing single and double substitutions and perturbatively included triple excitations [AE-CCSD(T)] in conjunction with a correlation-consistent double-ζ basis set (cc-pVDZ) by utilizing density functional theory (DFT) optimized geometries (M06-2X/cc-pVDZ) with zero-point vibrational energy (ZPVE) corrections. Exchange of the methoxy for a trifluoromethoxy group successfully prevents insertion and (o-trifluoromethoxy)benzaldehyde is produced instead; however, the carbene cannot be observed under these conditions. Thermal decomposition of (o-methoxyphenyl)glyoxylic acid in refluxing xylenes does not give the insertion product but yields o-anisaldehyde. This unanticipated outcome can be rationalized by protonation of the hydroxycarbene intermediate leading to the tautomeric formyl group. Thermochemical computations at M06-2X/cc-pVDZ in conjunction with a self-consistent solvent reaction field model support this suggested reaction pathway.

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13

Fan, Liangyou, Daryll Harrison, Liqun Deng, Tom K. Woo, David Swerhone, and Tom Ziegler. "A density functional study on olefin insertion and hydrogen transfer in the reaction between Cl2Ti+–ethyl and ethylene. Possible implications for the stereochemistry and chain termination in olefin polymerization." Canadian Journal of Chemistry 73, no. 7 (1995): 989–98. http://dx.doi.org/10.1139/v95-122.

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Calculations based on density functional theory have been carried out on the reaction between Cl2Ti+–ethyl (1) and ethylene. In this study 1 was taken as a model for the cationic metallocenes of group-4 elements, which have been developed by Kaminsky and Brintzinger as efficient catalysts for the polymerization of olefins. The ground state structure of 1 has a β-agostic conformation in which a single Cβ—H bond is directed towards the metal center. It was assumed that this conformation also serves as a model for the resting state of the growing chain attached to the cationic group-4 metallocenes between insertions. Two paths were considered for the reaction between 1 and ethylene. The first (2) has ethylene approaching the agostic Cβ—H bond, whereas ethylene in the second approach (3) attacks the Ti—Cα link from the side opposite to the Cβ—H bond. The front-side attack (2) results in a transfer of hydrogen from the β-carbon of ethyl to ethylene and represents a chain-terminating step with an activation energy of 5.3 kcal/mol. It was not possible to locate a path leading to olefin insertion from the front-side attack (2). The back-side attack (3) resulted readily in insertion with an activation energy of 3.9 kcal/mol. The study made use of full transition state optimization as well as a tracing of the reaction paths by the intrinsic reaction coordinate (IRC) method of Fukui. Previous investigations have all assumed that olefin insertion takes place via a front-side approach (2) based on the known stereochemistry of α-olefin polymerization. The present study suggests that insertion takes place by a back-side approach (3), and this suggestion is discussed in connection with the known stereochemistry of olefin polymerization. Keywords: Ziegler–Natta, olefin polymerization, density functional.

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14

Wen, Li-Rong, Ning-Ning Wang, Wu-Bo Du, Qiang Ma, Lin-Bao Zhang, and Ming Li. "Nickel-promoted oxidative domino Csp3–H/N–H bond double-isocyanide insertion reaction to construct pyrrolin-2-ones." Organic & Biomolecular Chemistry 19, no. 13 (2021): 2895–900. http://dx.doi.org/10.1039/d1ob00139f.

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15

Nistanaki, Sepand K., Chloe G. Williams, Benjamin Wigman, et al. "Catalytic asymmetric C–H insertion reactions of vinyl carbocations." Science 378, no. 6624 (2022): 1085–91. http://dx.doi.org/10.1126/science.ade5320.

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From the preparation of pharmaceuticals to enzymatic construction of natural products, carbocations are central to molecular synthesis. Although these reactive intermediates are engaged in stereoselective processes in nature, exerting enantiocontrol over carbocations with synthetic catalysts remains challenging. Many resonance-stabilized tricoordinated carbocations, such as iminium and oxocarbenium ions, have been applied in catalytic enantioselective reactions. However, their dicoordinated counterparts (aryl and vinyl carbocations) have not, despite their emerging utility in chemical synthesis. We report the discovery of a highly enantioselective vinyl carbocation carbon–hydrogen (C–H) insertion reaction enabled by imidodiphosphorimidate organocatalysts. Active site confinement featured in this catalyst class not only enables effective enantiocontrol but also expands the scope of vinyl cation C–H insertion chemistry, which broadens the utility of this transition metal–free C(sp 3 )–H functionalization platform.

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16

Solé, Daniel, Ferran Pérez-Janer, Arianna Amenta, M. Lluïsa Bennasar та Israel Fernández. "Site Selectivity in Pd-Catalyzed Reactions of α-Diazo-α-(methoxycarbonyl)acetamides: Effects of Catalysts and Substrate Substitution in the Synthesis of Oxindoles and β-Lactams". Molecules 24, № 19 (2019): 3551. http://dx.doi.org/10.3390/molecules24193551.

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The Pd-catalyzed intramolecular carbene C–H insertion of α-diazo-α-(methoxycarbonyl)acetamides to prepare oxindoles as well as β-lactams was studied. In order to identify what factors influence the selectivity of the processes, we explored how the reactions are affected by the catalyst type, using two oxidation states of Pd and a variety of ligands. It was found that, in the synthesis of oxindoles, ((IMes)Pd(NQ))2 can be used as an alternative to Pd2(dba)3 to catalyze the carbene CArsp2–H insertion, although it was less versatile. On the other hand, it was demonstrated that the Csp3–H insertion leading to β-lactams can be effectively promoted by both Pd(0) and Pd(II) catalysts, the latter being most efficient. Insight into the reaction mechanisms involved in these transformations was provided by DFT calculations.

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17

Zhang, Xinzhi, Yangyang Zhang, Cuijian Liang, and Jun Jiang. "Copper-catalyzed P–H insertion reactions of sulfoxonium ylides." Organic & Biomolecular Chemistry 19, no. 26 (2021): 5767–71. http://dx.doi.org/10.1039/d1ob00948f.

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18

Shaw, Jared T. "C–H Insertion Reactions of Donor/Donor Carbenes: Inception, Investigation, and Insights." Synlett 31, no. 09 (2020): 838–44. http://dx.doi.org/10.1055/s-0039-1691738.

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Insertion reactions of donor/donor carbenes have emerged from obscurity to become a versatile method for the synthesis of a variety of cyclic structures with excellent control of diastereo- and enantioselectivity. This Account describes the origin of this project as part of a natural product synthesis and the ensuing decade of reaction development that has resulted in new asymmetric methods as well as intriguing tangential observations.

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19

Zheng, Junhao, Zhen Hua Li, and Huadong Wang. "Addition of dihydrogen to a borylborenium center." Chemical Science 9, no. 6 (2018): 1433–38. http://dx.doi.org/10.1039/c7sc04987k.

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20

Venneri, Paul C., and John Warkentin. "Reaction of dimethoxycarbene with strained cyclic carbonyl compounds." Canadian Journal of Chemistry 78, no. 9 (2000): 1194–203. http://dx.doi.org/10.1139/v00-118.

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A cyclopropanone, a cyclopropenone, cyclobutanones, a cyclobutane-1,3-dione, and a cyclobutene-1,2-dione reacted with dimethoxycarbene to afford acetals of the next larger ring by formal insertion of the carbene into a CC bond α to the carbonyl group. When either of two saturated α-ring carbons could be involved in the process, the ring expansion was selective, affording primarily the product of apparent insertion into the more substituted ring bond. With 2,3-dimethoxycyclobutene-1,2-dione, insertion occurred between the carbonyl groups and with β-propiolactone it occurred at the lactone bond. β-Propiolactam, however, reacted by insertion of the carbene into the NH bond.Key words: β-propiolactone, cyclobutanone, cyclobutananedione, cyclopropanone, dialkoxycarbene.

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21

Feng, Jiajun, Xiangyan Yi, Yaofeng Fu, Yang Yu та Fei Huang. "Progress in N-H Insertion Reaction of α-Diazocarbonyl Compounds". Chinese Journal of Organic Chemistry 39, № 11 (2019): 3013. http://dx.doi.org/10.6023/cjoc201904044.

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22

Ohira, Susumu, Naoya Yoshihara, and Taisuke Hasegawa. "Synthesis of (−)-Gleenol via C-H Insertion Reaction of Alkylidenecarbene." Chemistry Letters 27, no. 8 (1998): 739–40. http://dx.doi.org/10.1246/cl.1998.739.

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23

Li, Pingfan. "Sulfur-Mediated Reactions through Sulfonium Salts and Ylides." Synlett 32, no. 13 (2021): 1275–80. http://dx.doi.org/10.1055/a-1409-0906.

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AbstractThis Account discusses several new reaction methods developed in our group that utilize sulfur-mediated reactions through sulfonium salts and ylides, highlighting the interplay of rational design and serendipity. Our initial goal was to convert aliphatic C–H bonds into C–C bonds site-selectively, and without the use of transition-metal catalysts. While a proof-of-concept has been achieved, this target is far from being ideally realized. The unexpected discovery of an anti-Markovnikov rearrangement and subsequent studies on difunctionalization of alkynes were much more straightforward, and eventually led to the new possibility of asymmetric N–H insertion of sulfonium ylides through Brønsted acid catalysis.1 Introduction2 Allylic/Propargylic C–H Functionalization3 Anti-Markovnikov Rearrangement4 Difunctionalization of Alkynes5 Asymmetric N–H Insertion of Sulfonium Ylides6 Conclusion

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24

Ahmadi, Fereshteh, and Ayoob Bazgir. "Synthesis of benzoimidazoquinazolines by cobalt-catalyzed isocyanide insertion–cyclization." RSC Advances 6, no. 66 (2016): 61955–58. http://dx.doi.org/10.1039/c6ra06828f.

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The synthesis of benzoimidazoquinazoline amines by the reaction of isocyanides and benzo[d]imidazol-anilines via a cobalt-catalyzed isocyanide insertion reaction into the two N–H active bonds is reported.

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25

Tyagi, Vikas, Rachel B. Bonn, and Rudi Fasan. "Intermolecular carbene S–H insertion catalysed by engineered myoglobin-based catalysts." Chemical Science 6, no. 4 (2015): 2488–94. http://dx.doi.org/10.1039/c5sc00080g.

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26

Jensen, Vidar R., and Per E. M. Siegban. "The Ziegler—Natta olefin insertion reaction for cationic metals." Chemical Physics Letters 212, no. 3-4 (1993): 353–61. http://dx.doi.org/10.1016/0009-2614(93)89337-h.

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27

Popov, Stasik, Brian Shao, Alex L. Bagdasarian, et al. "Teaching an old carbocation new tricks: Intermolecular C–H insertion reactions of vinyl cations." Science 361, no. 6400 (2018): 381–87. http://dx.doi.org/10.1126/science.aat5440.

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Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.

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28

Kuninobu, Yoichiro, Atsushi Kawata, Salprima S. Yudha, Hisatsugu Takata, Mitsumi Nishi, and Kazuhiko Takai. "Rhenium- and manganese-catalyzed carbon–carbon bond formation using 1,3-dicarbonyl compounds and alkynes." Pure and Applied Chemistry 82, no. 7 (2010): 1491–501. http://dx.doi.org/10.1351/pac-con-09-09-21.

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A rhenium complex, [ReBr(CO)3(thf)]2, catalyzed insertion of terminal alkynes into a C–H bond of active methylene sites of 1,3-dicarbonyl compounds. When a catalytic amount of isocyanide or molecular sieves was added to the reaction mixture, the reaction course changed markedly, and insertion of alkynes into a C–C single bond between α- and β-positions of cyclic and acyclic β-keto esters occurred. The formed acyclic δ-keto esters could be converted to 2-pyranones, which were applied to the synthesis of multisubstituted aromatic compounds via the Diels–Alder reaction and successive elimination of carbon dioxide. In the case of the rhenium-catalyzed reactions between terminal alkynes and β-keto esters without substituent at the α-position, tetrasubstituted benzenes were produced regioselectively by two-to-one reaction of the components. The yields of tetrasubstituted benzenes were improved by using a manganese catalyst.

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29

Tanabe, Yusuke, Yoshiyuki Mizuhata, and Norihiro Tokitoh. "Novel silacyclohexadienyl chromium and iron complexes bearing a bulky substituent on the central silicon atom." Pure and Applied Chemistry 82, no. 4 (2010): 879–90. http://dx.doi.org/10.1351/pac-con-09-10-08.

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Novel hydrido(silacyclohexadienyl)chromium complexes bearing a bulky substituent, Tbt (2,4,6-tris[bis(trimethylsilyl)methyl]phenyl), were synthesized using formal insertion reactions of Cr(0) into C–H or Si–H bond. When the reactions of 1-silacyclohexa-2,4-dienes bearing a hydroxy or chloro group on the silicon atom with [Cr(CH3CN)3(CO)3] were performed, the corresponding hydrido(1-silacyclohexa-2,4-dienyl) complexes were obtained as the sole product. A similar reaction of a hydrosilane having a similar skeleton with [Cr(CH3CN)3(CO)3] gave an unprecedented type of silacyclohexadienyl complex, hydrido(1-silacyclohexa-1,3-dienyl)chromium bearing a three-center bonding interaction among the silicon, hydrogen, and chromium atoms. These are the first syntheses of silacyclohexadienyl complexes by the formal insertion reaction toward the corresponding silacyclohexadienes. Furthermore, the isolation of the silacyclohexadienyl anion was achieved; it was applied to synthesis of the corresponding sandwich-type iron complex. Structures of the newly obtained complexes were revealed based on their NMR and IR spectroscopic data and X-ray diffraction study.

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30

Basab, Roy, Hatial Ishita, Ghosh Debaki, Sarathi Addy Partha, and Basak Amit. "Synthesis of bicyclic y-lactam derivatives by intramolecular carbene insertion and aza-Wittig reaction." Journal of Indian Chemical Society Vol. 90, Oct 2013 (2013): 1841–51. https://doi.org/10.5281/zenodo.5792069.

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Department of Chemistry, Indian Institute of Technology, Kharagpur-721 302, West Bengal, India <em>E-mail </em>: absk@chem.iitkgp.ernet.in <em>Manuscript received 27 June 2013, accepted 28 June 2013</em> A comparative study of the various methodologies to construct bicyclic \(\gamma\)-lactams is reported. Thus Rh<sup>II</sup> - catalyzed decomposition of 2-pyrrolidone and pyrrolidine derived diazomalonates were attempted to synthesize fused ylactams. Spectral evidences revealed the formation of diastereomeric alcohols instead of desired C-H or N-H insertion products, indicating significant conformational bias towards insertion process. On the other hand, the method involving the N-H insertion onto the lactam nitrogen of 2-pyrrolidone ring was successful. Intramolecular aza-Wittig reaction was also successfully explored to construct bicyclic \(\gamma\)-Iactam scaffolds. All the bicyclic analogues showed weak antibacterial activity against <em>\(S\). \(aureus\)</em> and <em>\(E\). \(coli\)</em>.

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31

Fernandez-Cestau, Julio, Luca Rocchigiani, Anna Pintus, Raquel J. Rama, Peter H. M. Budzelaar, and Manfred Bochmann. "Isocyanide insertion into Au–H bonds: first gold iminoformyl complexes." Chemical Communications 54, no. 81 (2018): 11447–50. http://dx.doi.org/10.1039/c8cc06409a.

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The reaction of gold hydrides with isocyanides leads to η<sup>1</sup>-iminoformyl complexes, the first example of an isocyanide insertion in gold chemistry. Key intermediates are gold(ii) isocyanide adducts.

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32

Hashikawa, Yoshifumi, Kazuro Kizaki, Takashi Hirose, and Yasujiro Murata. "An orifice design: water insertion into C60." RSC Advances 10, no. 66 (2020): 40406–10. http://dx.doi.org/10.1039/d0ra09067k.

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33

DeLuca, Ryan J., Benjamin J. Stokes, and Matthew S. Sigman. "The strategic generation and interception of palladium-hydrides for use in alkene functionalization reactions." Pure and Applied Chemistry 86, no. 3 (2014): 395–408. http://dx.doi.org/10.1515/pac-2014-5041.

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Abstract We review methods that our lab has developed for the generation of Pd-hydrides and the manipulation of these useful intermediates via β-hydride elimination and migratory insertion steps. For a given alkene functionalization reaction, careful understanding of the dynamics of β-hydride elimination, migratory insertion, and transmetallation have allowed for the selective functionalization of Pd-alkyl intermediates. This has afforded us a means by which to transpose palladium to a desired position on a substrate for subsequent functionalization, empowering a number of useful C–H, C–O, and C–C bond-forming reactions.

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34

Keyes, Lauren K., Angela D. K. Todd, Nick A. Giffin, et al. "Reaction of sterically encumbered phenols, TEMPO-H, and organocarbonyl insertion reactions with L-AlH2 (L = HC(MeCNDipp)2, Dipp = 2,6-diisopropylphenyl)." RSC Advances 7, no. 59 (2017): 37315–23. http://dx.doi.org/10.1039/c7ra06526d.

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35

Braunschweig, Holger, J. Oscar C. Jimenez-Halla, Krzysztof Radacki, and Rong Shang. "A metal-mediated boron-centred isomerisation reaction via C–H activation." Chemical Communications 51, no. 92 (2015): 16569–72. http://dx.doi.org/10.1039/c5cc07681a.

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The terminal borylene ligand is activated by Lewis bases to couple with terminal carbonyl ligands reversibly, initially forming a kinetic coupling product, which isomerises via a borylene migratory insertion to a cyclopentadienyl ligand C–H bond.

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36

Eremeyeva, Maria, Daniil Zhukovsky, Dmitry Dar’in та Mikhail Krasavin. "Preparation and in situ use of unstable N-alkyl α-diazo-γ-butyrolactams in RhII-catalyzed X–H insertion reactions". Beilstein Journal of Organic Chemistry 16 (2 квітня 2020): 607–10. http://dx.doi.org/10.3762/bjoc.16.55.

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N-Alkyl α-diazo-γ-butyrolactams, previously found to be unstable and to undergo unproductive dimerization to bishydrazones, were successfully converted immediately to various X–H insertion products with alcohols, aromatic amines and thiols via an in situ RhII-catalyzed reaction. With aliphatic amines or unreactive, sterically hindered anilines, the reactions tended to yield enamine adducts.

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37

Chow, Toby Wai-Shan, Guo-Qiang Chen, Yungen Liu, Cong-Ying Zhou, and Chi-Ming Che. "Practical iron-catalyzed atom/group transfer and insertion reactions." Pure and Applied Chemistry 84, no. 8 (2012): 1685–704. http://dx.doi.org/10.1351/pac-con-11-11-08.

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Iron-catalyzed reactions are receiving a surge of interest owing to the natural abundance and biocompatibility of Fe and the urge to develop practically useful sustainable catalysis for fine chemical industries. This article is a brief account of our studies on the C–O and C–N bond formation reactions catalyzed by Fe complexes supported by oligopyridine, macrocyclic tetraaza, and fluorinated porphyrin ligands. The working principle is the in situ generation of reactive Fe=O and Fe=NR intermediates supported by these oxidatively robust N-donor ligands for oxygen atom/nitrogen group transfer and insertion reactions. The catalytic reactions include C–H bond oxidation of saturated hydrocarbons (up to 87 % yield), epoxidation of alkenes (up to 96 % yield), cis-dihydroxylation of alkenes (up to 99 % yield), epoxidation–isomerization (E–I) reaction of aryl alkenes (up to 94 % yield), amination of C–H bonds (up to 95 % yield), aziridination of alkenes (up to 95 % yield), sulfimidation of sulfides (up to 96 % yield), and amide formation from aldehydes (up to 89 % yield). Many of these catalytic reactions feature high regio- and diastereoselectivity and/or high product yields and substrate conversions, and recyclability of the catalyst, demonstrating the applicability of Fe-catalyzed oxidative organic transformation reactions in practical organic synthesis.

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38

Keipour, Hoda, Angela Jalba, Nour Tanbouza, Virginie Carreras та Thierry Ollevier. "α-Thiocarbonyl synthesisviathe FeII-catalyzed insertion reaction of α-diazocarbonyls into S–H bonds". Organic & Biomolecular Chemistry 17, № 12 (2019): 3098–102. http://dx.doi.org/10.1039/c9ob00261h.

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39

Wang, Feiyu, Zhipeng Zhang, and Fei Huang. "Research Progress of O—H Insertion Reaction Based on Diazo Ester." Chinese Journal of Organic Chemistry 41, no. 1 (2021): 144. http://dx.doi.org/10.6023/cjoc202006014.

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40

Cheng, Qingqing, Huan Xu, Shoufei Zhu та Qilin Zhou. "Enantioselective Copper-Catalyzed B—H Bond Insertion Reaction of α-Diazoketones". Acta Chimica Sinica 73, № 4 (2015): 326. http://dx.doi.org/10.6023/a15020125.

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41

Guadagnini, Renee, and George C. Schatz. "Unusual Insertion Mechanism in the Reaction C(3P) + H2 → CH + H." Journal of Physical Chemistry 100, no. 49 (1996): 18944–49. http://dx.doi.org/10.1021/jp961164y.

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42

Lee, S. H., and K. Liu. "Direct mapping of insertion reaction dynamics: S(1D)+H2→SH+H." Applied Physics B 71, no. 5 (2000): 627–33. http://dx.doi.org/10.1007/s003400000386.

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43

Yang, Jingya, Ganggang Wang, Shuwen Chen та ін. "Catalyst-free, visible-light-promoted S–H insertion reaction between thiols and α-diazoesters". Organic & Biomolecular Chemistry 18, № 46 (2020): 9494–98. http://dx.doi.org/10.1039/d0ob02006k.

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44

Xu, Xiaofei, Chang Li, Zhihao Tao, and Yuanjiang Pan. "Aqueous hemin catalyzed sulfonium ylide formation and subsequent [2,3]-sigmatropic rearrangements." Green Chemistry 19, no. 5 (2017): 1245–49. http://dx.doi.org/10.1039/c6gc02681h.

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45

Liu, Zhenfeng, and Jianyong Liu. "DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O." Open Chemistry 8, no. 1 (2010): 223–28. http://dx.doi.org/10.2478/s11532-009-0118-8.

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AbstractThe mechanism of the dirhodium tetracarboxylate-catalyzed O-H insertion reaction of diazomethane and methyl diazoacetate with H2O has been studied in detail using DFT calculations. The rhodium catalyst and a diazo compound couple to form a rhodiumcarbene complex. Of two reaction pathways of the Rh(II)-carbene complex with H2O, the stepwise pathway is more preferable than the concerted one. Formation of a Rh(II) complex-associated oxonium ylide is an exothermal process, and direct decomposition of the ylide gives a very high barrier. The high barriers for the 1,2-H shift of Rh(II) complex-associated oxonium ylides make the ylides become stable intermediates in both reactions, especially for the reactions in solution. Difficulty in formation of a free oxonium ylide supports experimental results, indicating that the Rh(II) complex-catalyzed nucleophilic addition of a diazo compound proceeds via a Rh(II) complex-associated oxonium ylide rather than via a free oxonium ylide.

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46

Hilinski, Michael, Shea Johnson, and Logan Combee. "Organocatalytic Atom-Transfer C(sp3)–H Oxidation." Synlett 29, no. 18 (2018): 2331–36. http://dx.doi.org/10.1055/s-0037-1610432.

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Predictably site-selective catalytic methods for intermolecular C(sp3)–H hydroxylation and amination hold great promise for the synthesis and late-stage modification of complex molecules. Transition-metal catalysis has been the most common approach for early investigations of this type of reaction. In comparison, there are far fewer reports of organocatalytic methods for direct oxygen or nitrogen insertion into C–H bonds. Herein, we provide an overview of early efforts in this area, with particular emphasis on our own recent development of an iminium salt that catalyzes both oxygen and nitrogen insertion.1 Introduction2 Background: C–H Oxidation Capabilities of Heterocyclic Oxidants3 Oxaziridine-Mediated Catalytic Hydroxylation4 Dioxirane-Mediated Catalytic Hydroxylation5 Iminium Salt Catalysis of Hydroxylation and Amination6 Conclusion and Outlook

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47

Becerra, Rosa, Sergey E. Boganov, Mikhail P. Egorov, Valery I. Faustov, Oleg M. Nefedov, and Robin Walsh. "The insertion of germylene into the HH bond; rate constant limits and thermochemistry. Ab initio and DFT calculations on the reactions of GeH2 and SiH2 with H2." Canadian Journal of Chemistry 78, no. 11 (2000): 1428–33. http://dx.doi.org/10.1139/v00-106.

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The technique of laser flash photolysis in the gas-phase has been used to set limits on the rate constants for the bimolecular reaction of germylene (GeH2) with deuterium (D2) at both ambient and elevated temperatures (585 K). These limits show that the activation energy for the insertion of GeH2 into the HH bond is at least 19 (±6) kJ mol1. Thermochemical arguments place the activation energy approximately in the range 6384 kJ mol1. DFT B3LYP/6-311++G(3df,2pd) and ab initio QCISD(T)/6-311G++(3df,2pd)//QCISD/6-311G(d,p) calculations have been carried out on the potential energy surfaces of reactions ZH2 + H2 [Formula: see text] ZH4 (Z= Ge, Si). Both methods predict the same mechanisms for germylene and silylene insertion which include formation of loose prereaction complexes and transition states of similar structure. The prereaction complex is only about half as strong in the case of germylene (ΔH (298 K) = 9 (11) kJ mol1) as in the case of silylene (ΔH (298 K) = 16 (21) kJ mol1) (QCISD values cited with B3LYP values in parentheses). The differences in activation energies are even more significant. Germylene insertion has a very high barrier of 58 (56) kJ mol1 compared to that of silylene 13 (6) kJ mol1. Calculated activation parameters for both reactions are in reasonable consistency with experimental results. Reasons for the enhanced HH insertion barrier for germylene compared with silylene are discussed.Key words: laser flash photolysis, germylene, silylene, deuterium, activation energy, thermochemistry, ab initio calculation, DFT B3LYP calculation.

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48

Nakagawa, Yoko, Soda Chanthamath, Ikuhide Fujisawa, Kazutaka Shibatomi, and Seiji Iwasa. "Ru(ii)-Pheox-catalyzed Si–H insertion reaction: construction of enantioenriched carbon and silicon centers." Chemical Communications 53, no. 26 (2017): 3753–56. http://dx.doi.org/10.1039/c7cc01070b.

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49

Ding, Dong, Xiaobing Lv, Jian Li, Lin Qiu, Guangyang Xu, and Jiangtao Sun. "A Pd-catalyzed cascade reaction of N–H insertion and oxidative dehydrogenative aromatization: a new entry to 2-amino-phenols." Org. Biomol. Chem. 12, no. 24 (2014): 4084–88. http://dx.doi.org/10.1039/c4ob00652f.

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50

Zhang, Qingjun, Pengyuan Shi, and Aiwu Zeng. "Carboxylate-Assisted Carboxylation of Thiophene with CO2 in the Solvent-Free Carbonate Medium." Catalysts 12, no. 4 (2022): 369. http://dx.doi.org/10.3390/catal12040369.

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Direct carboxylation of thiophene with CO2 has been achieved under a relatively mild solvent-free carbonate and carboxylate medium. This base-mediated medium can cleave the very weakly acidic C–H bond without using other limiting reagents, which is one indispensable step in the carboxylation reaction. Product yield varies with different carboxylate salts, and cesium pivalate is the most suitable base additive among targeted simple carboxylate salts. Furthermore, the detailed mechanism of this carboxylation reaction is studied, which involves initial proton abstraction, rendered by carbonate and C–C bond formation, by inserting CO2. The activation energy barrier of the C–H activation step is higher than the following CO2 insertion step, whether for the formation of the mono- and/or di-carboxylate, which indicates that the C–H deprotonation induced by the base is slow and the resulting carbon-centered nucleophile reacts rapidly with CO2.

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