Academic literature on the topic 'Secondary alkyl halide'

Akiya Ogawa of Osaka Prefecture University found (Tetrahedron Lett. 2010, 51, 6580) that the Sm-mediated reductive coupling of a halide 1 with CO2 to give the carboxylic acid 2 was strongly promoted by visible light. Gregory C. Fu of MIT designed (Angew. Chem. Int. Ed. 2010, 49, 6676) a Ni catalyst for the coupling of a primary borane 4 with a secondary alkyl halide 3. James P. Morken of Boston College devised (Org. Lett. 2010, 12, 3760) conditions for the carbonylative conjugate addition of a dialkyl zinc to an enone 6 to give the 1,4-dicarbonyl product 7. Louis Fensterbank of the Institut Parisien de Chimie Moléculaire developed (Angew. Chem. Int. Ed. 2010, 49, 8721; not illustrated) a protocol for the conjugate addition of alkyl boranes to enones. Hyunik Shin of LG Life Science, Daejeon, and Sang-gi Lee of Ewha Womans University showed (Tetrahedron Lett. 2010, 51, 6893) that the intermediate from Blaise homologation of a nitrile 8 was a powerful nucleophile, smoothly opening an epoxide 10 to deliver 11. Sébastien Reymond and Janine Cossy of ESPCI ParisTech found (J. Org. Chem. 2010, 75, 5151) that FeCl3 smoothly catalyzed the coupling of an alkenyl Grignard 13 with the primary iodide 12. The Ti-mediated coupling of an alkyne 16 with an allylic alkoxide 15 (J. Am. Chem. Soc. 2010, 132, 9576) developed by Glenn C. Micalizio of Scripps/Florida was the key step in the total synthesis (J. Am. Chem. Soc. 2010, 132, 11422) of lehualide B. Huanfeng Jiang of the South China University of Technology observed (Chem. Commun. 2010, 46, 8049) that KI added to a bromoalkyne 18 to give the dihalide 19 with high geometric control. Haruhiko Fuwa of Tohoku University improved (Org. Lett. 2010, 12, 5354) the selective hydroiodination of a methyl alkyne 20 to 21. Takuya Kurahashi and Seijiro Matsubara of Kyoto University devised (Chem. Commun. 2010, 46, 8055) the Ni-catalyzed three-component coupling of an alkyne 22, methyl acrylate 23, and phenyl isocyanate to give the doubly homologated lactam 24. Patrick H. Toy of the University of Hong Kong showed (Synlett 2010, 1997; Org. Lett. 2010, 12, 4996 for a polymer with covalently attached base) that resin-bound triphenylphosphine participated efficiently in the Wittig coupling of 26 with an aldehyde 25.

Xile Hu of the Ecole Polytechnique Fédérale de Lausanne optimized (J. Am. Chem. Soc. 2011, 133, 7084) a Ni catalyst for the coupling of a Grignard reagent 2 with a secondary alkyl halide 1. Duk Keun An of Kangwon National University devised (Tetrahedron Lett. 2011, 52, 1718; Chem. Commun. 2011, 47, 3281) a strategy for the reductive coupling of an ester 4 with a Grignard reagent 2 to give the secondary alcohol. Daniel J. Weix of the University of Rochester added (Org. Lett. 2011, 13, 2766) the halide 7 in a conjugate sense to the bromoenone 6, setting the stage for further organometallic coupling. James Y. Becker of the Ben-Gurion University of the Negev effected (J. Org. Chem. 2011, 76, 4710) Kolbe coupling of the silyl acid 9 to give the decarboxylated dimer 10. Shi-Kai Tian of USTC Hefei showed (Chem. Commun. 2011, 47, 2158) that depending on the sulfonyl group used, the coupling of 11 with 12 could be directed cleanly toward either the Z or the E product. Yoichiro Kuninobu and Kazuhiko Takai of Okayama University added (Org. Lett. 2011, 13, 2959) the sulfonyl ketone 14 to the alkyne 13 to form the trisubstituted alkene 15. Jianbo Wang of Peking University assembled (Angew. Chem. Int. Ed. 2011, 50, 3510) the trisubstituted alkene 18 by adding the diazo ester 16 to the alkyne 17. Gangguo Zhu of Zhejiang Normal University constructed (J. Org. Chem. 2011, 76, 4071) the versatile tetrasubstituted alkene 21 by adding the chloroalkyne 19 to acrolein 20. Other more substituted acceptors worked as well. Chunxiang Kuang of Tongji University and Qing Yang of Fudan University effected (Tetrahedron Lett. 2011, 52, 992) elimination of 22 to 23 by stirring with Cs2CO3 at 115°C in DMSO overnight. Toshiaki Murai of Gifu University created (Chem. Lett. 2011, 40, 70) a propargyl anion by condensing 24 with 25 then adding 26. Xiaodong Shi of West Virginia University found (Org. Lett. 2011, 13, 2618) that the enantiomerically enriched propargyl ether 29 could be rearranged to the trisubsituted allene 30 with retention of the ee and with high de.

Carlo Siciliano and Angelo Liguori of the Università della Calabria showed (J. Org. Chem. 2012, 77, 10575) that an amino acid 1 could be both protected and activated with Fmoc-Cl, so subsequent exposure to diazomethane delivered the Fmoc-protected diazo ketone 2. Pei-Qiang Huang of Xiamen University activated (Angew. Chem. Int. Ed. 2012, 51, 8314) a secondary amide 3 with triflic anhydride, then added an alkyl Grignard reagent with CeCl3 to give an intermediate that was reduced to the amine 4. John C. Walton of the University of St. Andrews found (J. Am. Chem. Soc. 2012, 134, 13580) that under irradiation, titania could effect the decarboxylation of an acid 5 to give the dimer 6. Jin Kun Cha of Wayne State University demonstrated (Angew. Chem. Int. Ed. 2012, 51, 9517) that a zinc homoenolate derived from 7 could be transmetalated, then coupled with an electrophile to give the alkylated product 8. The Ramberg-Bäcklund reaction is an underdeveloped method for the construction of alkenes. Adrian L. Schwan of the University of Guelph showed (J. Org. Chem. 2012, 77, 10978) that 10 is a particularly effective brominating agent for this transformation. Daniel J. Weix of the University of Rochester coupled (J. Org. Chem. 2012, 77, 9989) the bromide 12 with the allylic carbonate 13 to give 14. The Julia-Kocienski coupling, illustrated by the addition of the anion of 16 to the aldehyde 15, has become a workhorse of organic synthesis. In general, this reaction is E selective. Jirí Pospísil of the University Catholique de Louvain demonstrated (J. Org. Chem. 2012, 77, 6358) that inclusion of a K+-sequestering agent switched the selectivity to Z. Yoichiro Kuninobu, now at the University of Tokyo, and Kazuhiko Takai of Okayama University constructed (Org. Lett. 2012, 14, 6116) the tetrasubstituted alkene 20 with high geometric control by the Re-catalyzed addition of 19 to the alkyne 18. André B. Charette of the Université de Montréal converted (Org. Lett. 2012, 14, 5464) the allylic halide 21 to the alkyne 22 by displacement with iodoform followed by elimination. In an elegant extension of his studies with alkyl tosylhydrazones, Jianbo Wang of Peking University added (J. Am. Chem. Soc. 2012, 134, 5742) an alkyne 24 to 23 to give 25.

Daniel J. Weix of the University of Rochester effected (Org. Lett. 2012, 14, 1476) the in situ reductive coupling of an alkyl halide 2 with an acid chloride 1 to deliver the ketone 3. André B. Charette of the Université de Montréal (not illustrated) developed (Nature Chem. 2012, 4, 228) an alternative route to ketones by the coupling of an organometallic with an in situ-activated secondary amide. Mahbub Alam and Christopher Wise of the Merck, Sharpe and Dohme UK chemical process group optimized (Org. Process Res. Dev. 2012, 16, 453) the opening of an epoxide 4 with a Grignard reagent 5. Ling Song of the Fujian Institute of Research on the Structure of Matter optimized (J. Org. Chem. 2012, 77, 4645) conditions for the 1,2-addition of a Grignard reagent (not illustrated) to a readily enolizable ketone. Wei-Wei Liao of Jilin University conceived (Org. Lett. 2012, 14, 2354) of an elegant assembly of highly functionalized quaternary centers, as illustrated by the conversion of 7 to 8. Antonio Rosales of the University of Granada and Ignacio Rodríguez-García of the University of Almería prepared (J. Org. Chem. 2012, 77, 4171) free radicals by reduction of an ozonide 9 in the presence of catalytic titanocene dichloride. In the absence of the acceptor 10, the dimer of the radical was obtained, presenting a simple alternative to the classic Kolbe coupling. Marc L. Snapper of Boston College found (Eur. J. Org. Chem. 2012, 2308) that the difficult ketone 12 could be methylenated following a modified Peterson protocol. Yoshito Kishi of Harvard University optimized (Org. Lett. 2012, 14, 86) the coupling of 15 with 16 to give 17. Masaharu Nakamura of Kyoto University devised (J. Org. Chem. 2012, 77, 1168) an iron catalyst for the coupling of 18 with 19. The specific preparation of trisubsituted alkenes is an ongoing challenge. Quanri Wang of Fudan University and Andreas Goeke of Givaudan Shanghai fragmented (Angew. Chem. Int. Ed. 2012, 51, 5647) the ketone 21 by exposure to 22 to give the macrolide 23 with high stereocontrol.

Mohammad Navid Soltani Rad of Shiraz University of Technology has shown (Tetrahedron Lett. 2007, 48, 6779) that with tosylimidazole (TsIm) activation in the presence of NaCN, primary, secondary and tertiary alcohols are converted into the corresponding nitriles. Gregory C. Fu of MIT has devised (J. Am. Chem. Soc. 2007, 129, 9602) a Ni catalyst that mediated the coupling of sp3-hybridized halides such as 3 with sp3-hybridized organoboranes such as 4, to give 5. Usually, carbanions with good leaving groups in the beta position do not couple efficiently, but just eliminate. Scott D. Rychnovsky of the University of California, Irvine has found (Organic Lett . 2007, 9, 4757) that initial protection of 6 as the alkoxide allowed smooth reduction of the sulfide and addition of the derived alkyl lithium to the amide 7 to give 8. Doubly-activated Michael acceptors such as 11 are often too unstable to isolate. J. S. Yadav of the Indian Institute of Chemical Technology, Hyderabad has shown (Tetrahedron Lett. 2007, 48, 7546) that Baylis-Hillman adducts such as 9 can be oxidized in situ, with concomitant Sakurai addition to give 12. Rather than use the usual Li or Na or K enolate, Don M. Coltart of Duke University has found (Organic Lett. 2007, 9, 4139) that ketones such as 13 will condense with amides such as 14 to give the diketone 15 on exposure to MgBr2. OEt2 and i -Pr2 NEt. Simultaneously, Gérard Cahiez of the Université de Cergy (Organic Lett. 2007, 9, 3253) and Janine Cossy of ESPCI Paris (Angew. Chem. Int. Ed. 2007, 46, 6521) reported that Fe salts will catalyze the coupling of sp2 -hybridized Grignard reagents such as 17 with alkyl halides. John Montgomery of the University of Michigan has described (J. Am. Chem. Soc. 2007, 129, 9568) the Ni-mediated regio- and enantioselective addition of an alkynes 20 to an aldehyde 19 to give the allylic alcohol 21. In a third example of sp2 - sp3 coupling, Troels Skrydstrup of the University of Aarhus has established (J. Org. Chem. 2007, 72, 6464) that Negishi coupling with alkenyl phosponates such as 23 proceeded efficiently.

Jeffrey C. Pelletier of Wyeth Research, Collegeville, PA has developed (Tetrahedron Lett. 2007, 48, 7745) a easy work-up Mitsunobu procedure for the conversion of a primary alcohol such as 1 to the corresponding primary amine 2. Shlomo Rozen of Tel-Aviv University has taken advantage (J. Org. Chem. 2007, 72, 6500) of his own method for oxidation of a primary amine to the nitro compound to effect net conversion of an amino ester 3 to the alkylated amino ester 5. Note that the free amine of 3 or 5 would react immediately with methyl iodide. Keith A. Woerpel of the University of California, Irvine has uncovered (J. Am. Chem. Soc. 2007, 129, 12602) a Cu catalyst that, with 7, effected direct conversion of silyl ethers such as 6 to the allyl silane 8. An Ag catalyst gave 9, which also shows arllyl silane reactivity. Biswanath Das of the Indian Institute of Chemical Technology, Hyderabad has established (Tetrahedron Lett. 2007, 48, 6681) a compact procedure for the direct conversion of an aromatic aldehyde such as 10 to the benzylic halide 11. This will be especially useful for directly generating benzylic halides that are particularly reactive. α-Sulfinylation of ketones often requires intial generation of the enolate. J. S. Yadav, also of the Indian Institute of Chemical Technology, Hyderabad, has devised (Tetrahedron Lett. 2007, 48, 5243) an oxidative protocol for installing sulfur adjacent to a ketone. In a related development, Richard S. Grainger of the University of Birmingham has established (Angew. Chem. Int. Ed. 2007, 46, 5377) a simple procedure for the conversion of thio esters such as 14 to the corresponding ketone 16. Yoshiya Fukumoto of Osaka University has shown (J. Am. Chem. Soc. 2007, 129, 13792) that a terminal alkyne 17 can be directly converted into the enamine 18 by Rh-catalyzed addition of a secondary amine. Lukas Hintermann and Carsten Bolm of RWTH Aachen have found (J. Org. Chem. 2007, 72, 5704) that inclusion of water gave the aldehyde, which could be oxidized with the residual Ru catalyst to the acid.

Yuqing Hou of Southern Illinois University found (J. Org. Chem. 2009, 74, 6362) that the peroxy ether 2 served effectively to directly transfer a methoxy group to the lithiated 1 to give 3. Wanzhi Chen of Zhejiang University, Xixi Campus, showed (J. Org. Chem. 2009, 74, 7203) that pyrimidines such as 4, readily prepared from the corresponding phenol, underwent smooth Pd-catalyzed ortho acetoxylation. Trond Vidar Hansen of the University of Oslo observed (Tetrahedron Lett. 2009, 50, 6339) that simple electrophilic formylation of phenols such as 6 also proceeded with high ortho selectivity. Kyung Woon Jung of the University of Southern California optimized (J. Org. Chem. 2009, 74, 6231) the Rh catalyst for ortho C-H insertion, converting 8 into 9. Jin-Quan Yu of Scripps/La Jolla devised (Science 2010, 327, 315) a protocol for carboxy-directed catalytic ortho palladation that allowed subsequent Heck coupling, transforming 10 into 11. Norikazu Miyoshi of the University of Tokushima established (Chem. Lett. 2009, 38, 996) that in situ generated strontium alkyls added 1,6 to benzoic acid 13, to give, after mild oxidative workup, the 4-alkyl benzoic acid 15. Amin Zarei of Islamic Azad University showed (Tetrahedron Lett. 2009, 50, 4443) that their previously developed protocol for preparing stable diazonium silica sulfates could be extended to the preparation of an aryl azide such as 17. Stephen L. Buchwald of MIT developed (J. Am. Chem. Soc. 2009, 131, 12898) a Pd-mediated protocol for the conversion of aryl chlorides to the corresponding nitro aromatics. Virgil Percec of the University of Pennsylvania has also reported (Organic Lett. 2009, 11, 4974) the conversion of an aryl chloride to the borane, and Guy C. Lloyd-Jones has described (Angew. Chem. Int. Ed. 2009, 48, 7612) the conversion of phenols to the corresponding thiols. Kwang Ho Song of Korea University and Sunwoo Lee of Chonnam National University demonstrated (J. Org. Chem. 2009, 74, 6358) that the Ni-mediated homologation of aryl halides worked with a variety of primary and secondary formamides. Kwangyong Park of Chung-Ang University observed (J. Org. Chem. 2009, 74, 9566) that Ni catalysts also mediated the coupling of Grignard reagents with the tosylate 22 not in the usual way but with the C-S bond to give 23.