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1

Tlais, Sami F., and Gregory B. Dudley. "On the proposed structures and stereocontrolled synthesis of the cephalosporolides." Beilstein Journal of Organic Chemistry 8 (August 14, 2012): 1287–92. http://dx.doi.org/10.3762/bjoc.8.146.

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The synthesis of four candidate stereoisomers of cephalosporolide H is described, made possible by a zinc-chelation strategy for controlling the stereochemistry of oxygenated 5,5-spiroketals. The same strategy likewise enables the first stereocontrolled synthesis of cephalosporolide E, which is typically isolated and prepared admixed with its spiroketal epimer, cephalosporolide F.
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2

Brimble, Margaret A., and Seng H. Chan. "Synthesis of 7-Methoxy-3′,4′,5′,6′-tetrahydrospiro-[isobenzofuran-1(3H),2′-pyran]-3-one and 5,7-Dimethoxy-3′,4′,5′,6′-tetrahydrospiro[isobenzofuran-1(3H),2′-pyran]-3-one." Australian Journal of Chemistry 51, no. 3 (1998): 235. http://dx.doi.org/10.1071/c97193.

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The synthesis of novel aryl spiroketals, which contain a similar substitution pattern to that present in the antifungal agents the papulacandins, is described. Thus, spiroketal (7) was obtained from acid-catalysed cyclization of the keto alcohol (13), and spiroketal (8) was obtained from acid-catalysed cyclization of keto alcohols (12) and (19). Keto alcohols (12), (13) and (19) in turn were prepared by ortho-directed lithiation of amides (10), (11) and oxazoline (17) respectively, followed by reaction with δ-valerolactone. Substitution of the aromatic ring occurred at the sterically hindered
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3

Messerle, Barbara A., and Khuong Q. Vuong. "Synthesis of spiroketals by iridium-catalyzed double hydroalkoxylation." Pure and Applied Chemistry 78, no. 2 (2006): 385–90. http://dx.doi.org/10.1351/pac200678020385.

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A highly efficient approach to the synthesis of spiroketals involves the double cyclization of alkynyl diols using transition-metal catalysts. The iridium complex [Ir(PyP)(CO)2]BPh4 where PyP = 1-[(2-diphenylphosphino)ethyl]pyrazole is an effective catalyst for promoting the formation of spiroketals via this double hydroalkoxylation reaction. The complex promotes the formation of a series of spiroketal products from alkynyl diol starting materials such as 3-ethynylpentane-1,5-diol and 2-(4-hydroxybut-1-ynyl)benzyl alcohol. Stereoselective cyclization occurs for 3-ethynylpentane-1,5-diol, 3-eth
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4

Tlais, Sami F., and Gregory B. Dudley. "A gold-catalyzed alkyne-diol cycloisomerization for the synthesis of oxygenated 5,5-spiroketals." Beilstein Journal of Organic Chemistry 7 (May 4, 2011): 570–77. http://dx.doi.org/10.3762/bjoc.7.66.

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A highly efficient synthesis of oxygenated 5,5-spiroketals was performed towards the synthesis of the cephalosporolides. Gold(I) chloride in methanol induced the cycloisomerization of a protected alkyne triol with concomitant deprotection to give a strategically hydroxylated 5,5-spiroketal, despite the potential for regiochemical complications and elimination to furan. Other late transition metal Lewis acids were less effective. The use of methanol as solvent helped suppress the formation of the undesired furan by-product. This study provides yet another example of the advantages of gold catal
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5

Čikoš, Ana, Irena Ćaleta, Dinko Žiher, et al. "Structure and conformational analysis of spiroketals from 6-O-methyl-9(E)-hydroxyiminoerythronolide A." Beilstein Journal of Organic Chemistry 11 (August 19, 2015): 1447–57. http://dx.doi.org/10.3762/bjoc.11.157.

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Three novel spiroketals were prepared by a one-pot transformation of 6-O-methyl-9(E)-hydroxyiminoerythronolide A. We present the formation of a [4.5]spiroketal moiety within the macrolide lactone ring, but also the unexpected formation of a 10-C=11-C double bond and spontaneous change of stereochemistry at position 8-C. As a result, a thermodynamically stable structure was obtained. The structures of two new diastereomeric, unsaturated spiroketals, their configurations and conformations, were determined by means of NMR spectroscopy and molecular modelling. The reaction kinetics and mechanistic
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6

McLeod, Michael C., Margaret A. Brimble, Dominea C. K. Rathwell, Zoe E. Wilson, and Tsz-Ying Yuen. "Synthetic approaches to [5,6]-benzannulated spiroketal natural products." Pure and Applied Chemistry 84, no. 6 (2011): 1379–90. http://dx.doi.org/10.1351/pac-con-11-08-06.

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Studies toward the synthesis of three biologically active [5,6]-benzannulated spiroketal natural products are described. The first total synthesis of paecilospirone is reported, employing a late-stage, pH-neutral spiroketalization. A formal synthesis of γ-rubromycin is described, where the spiroketal moiety is formed by delicate manipulation of the electronic properties of the spirocyclization precursor. Finally, model work toward the total synthesis of berkelic acid is summarized, introducing a novel Horner–Wadsworth–Emmons/oxa-Michael (HWE/oxa-M) cascade to access the spiroketal precursor.
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7

Quayle, Peter, Jeremy C. Conway, Andrew C. Regan, and Christopher J. Urch. "A Palladium Mediated Spiroketal Synthesis." HETEROCYCLES 67, no. 1 (2006): 85. http://dx.doi.org/10.3987/com-05-s(t)20.

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8

Elsley, David A., Donald MacLeod, John A. Miller, Peter Quayle, and Gareth M. Davies. "A palladium mediated spiroketal synthesis." Tetrahedron Letters 33, no. 3 (1992): 409–12. http://dx.doi.org/10.1016/s0040-4039(00)74144-x.

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9

Ramakrishna, Bandi, and Perali Ramu Sridhar. "Stereoselective synthesis of 1,6-dioxaspirolactones from spiro-cyclopropanecarboxylated sugars: total synthesis of dihydro-pyrenolide D." RSC Advances 5, no. 11 (2015): 8142–45. http://dx.doi.org/10.1039/c4ra16753h.

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A one-pot protocol for the stereoselective construction of γ-spiroketal γ-lactone frameworks from sugar derived spiro-cyclopropanecarboxylic acids involving a ring enlargement and cyclization reaction is revealed.
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10

Conway, Jeremy C., Peter Quayle, Andrew C. Regan, and Christopher J. Urch. "Palladium mediated spiroketal synthesis: application to pheromone synthesis." Tetrahedron 61, no. 50 (2005): 11910–23. http://dx.doi.org/10.1016/j.tet.2005.09.055.

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11

Prusov, Evgeny V. "Synthesis of the spiroketal core of integramycin." Beilstein Journal of Organic Chemistry 9 (November 12, 2013): 2446–50. http://dx.doi.org/10.3762/bjoc.9.282.

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A concise synthetic strategy towards the spiroketal core of the HIV-integrase inhibitor integramycin (1) was developed. The required ketone precursor was efficiently constructed from two simple and easily accessible subunits by means of a hydrozirconation/copper catalyzed acylation reaction. The effects of different protecting groups on the spiroketalization step were also investigated.
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12

Reinus, Brandon J., and Sean M. Kerwin. "N-Alkynyl Pyrrole Based Total Synthesis of Shensongine A." Synthesis 51, no. 21 (2019): 4085–105. http://dx.doi.org/10.1055/s-0037-1611904.

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A copper-catalyzed N-alkynylation of pyrrole and a gold-catalyzed spiroketalization were key steps in the total synthesis of the pyrrole spiroketal alkaloid shensongine A. The preparation of this alkaloid is concise and amenable to the rapid synthesis of a diverse library of compounds.
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13

Commandeur, Malgorzata, Claude Commandeur, and Janine Cossy. "Spiroketals: Toward the synthesis of 39-oxobistramide K." Pure and Applied Chemistry 84, no. 7 (2012): 1567–74. http://dx.doi.org/10.1351/pac-con-11-09-06.

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An advanced spiroketal intermediate toward the synthesis of 39-oxobistramide K was prepared, fragment C14–C40. This fragment was obtained in 19 steps with an overall yield of 6.2 % using a FeCl3-catalyzed spiroketalization as the key step.
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14

Crimmins, Michael, and Adam Azman. "A Modular, Stereoselective Approach to Spiroketal Synthesis." Synlett 23, no. 10 (2012): 1489–92. http://dx.doi.org/10.1055/s-0031-1290670.

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15

ELSLEY, D. A., D. MACLEOD, J. A. MILLER, P. QUAYLE, and G. M. DAVIES. "ChemInform Abstract: A Palladium-Mediated Spiroketal Synthesis." ChemInform 23, no. 33 (2010): no. http://dx.doi.org/10.1002/chin.199233190.

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16

Ota, Koichiro, Hiroaki Miyaoka, Yoshiyori Hara, and Kazuo Kamaike. "Total Synthesis of Ascospiroketal B." Synlett 31, no. 17 (2020): 1730–34. http://dx.doi.org/10.1055/s-0040-1706405.

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An enantioselective total synthesis of the marine tricyclic polyketide ascospiroketal B, previously isolated from the marine-derived fungus Ascochyta salicorniae, was accomplished in 21 steps by using an improved route. The intriguing 5,5-spiroketal-cis-fused-γ-lactone core was constructed through rearrangement of an epoxide, in conjunction with an acid-mediated spiroketalization.
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17

Tomas, Loic, Benjamin Bourdon, Jean Claude Caille, David Gueyrard, and Peter G. Goekjian. "A Concise and Efficient Synthesis of Spiroketals - Application to the Synthesis of SPIKET-P and a Spiroketal fromBactroceraSpecies." European Journal of Organic Chemistry 2013, no. 5 (2013): 915–20. http://dx.doi.org/10.1002/ejoc.201201199.

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18

Gillard, Rachel M., and Margaret A. Brimble. "Benzannulated spiroketal natural products: isolation, biological activity, biosynthesis, and total synthesis." Organic & Biomolecular Chemistry 17, no. 36 (2019): 8272–307. http://dx.doi.org/10.1039/c9ob01598a.

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19

Taber, Douglass F., Jean-Michel Joerger, and Karen V. Taluskie. "Toward the total synthesis of ritterazine N." Pure and Applied Chemistry 80, no. 5 (2008): 1141–48. http://dx.doi.org/10.1351/pac200880051141.

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Zr-mediated equilibrating cyclocarbonylation of a designed triene led with high diastereocontrol to the ABC 6-6-5 tricyclic core of ritterazine N. The 5-5 EF spiroketal side chain of ritterazine N was prepared by equilibrating cyclization of an acyclic keto diol. The two components were coupled, and the D ring was assembled by intramolecular aldol condensation.
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20

Vidari, Giovanni, Maurizio Franzini, Luigi Garlaschelli, and Antonietta Maronati. "Diastereoselective synthesis of the saponaceolide tricyclic spiroketal substructure." Tetrahedron Letters 34, no. 16 (1993): 2685–88. http://dx.doi.org/10.1016/s0040-4039(00)77656-8.

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21

Rosenblum, Stuart B., and Ron Bihovsky. "Synthesis of the papulacandin C-arylglucosyl spiroketal nucleus." Journal of the American Chemical Society 112, no. 7 (1990): 2746–48. http://dx.doi.org/10.1021/ja00163a042.

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22

Ley, Steven V., Andrew Madin та Nathaniel J. T. Monck. "Total synthesis of the spiroketal macrolide (+) milbemycin α1". Tetrahedron Letters 34, № 46 (1993): 7479–82. http://dx.doi.org/10.1016/s0040-4039(00)60158-2.

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23

Wipf, Peter, та Jae-Kyu Jung. "Total Synthesis of the Spiroketal Naphthoquinone (±)-Diepoxin σ". Journal of Organic Chemistry 64, № 4 (1999): 1092–93. http://dx.doi.org/10.1021/jo9823691.

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24

Crimmins, Michael T., and Rosemary O'Mahony. "Synthesis of the spiroketal fragment of avermectin B1b." Tetrahedron Letters 30, no. 44 (1989): 5993–96. http://dx.doi.org/10.1016/s0040-4039(01)93836-5.

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25

Yadav, Jhillu S., N. Mallikarjuna Reddy, Md Ataur Rahman, and Attaluri R. Prasad. "Synthesis of the Spiroketal Fragment of (-)-Ushikulide A." European Journal of Organic Chemistry 2014, no. 25 (2014): 5574–81. http://dx.doi.org/10.1002/ejoc.201402196.

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26

Verano, Alyssa L., and Derek S. Tan. "Family-level stereoselective synthesis and biological evaluation of pyrrolomorpholine spiroketal natural product antioxidants." Chemical Science 8, no. 5 (2017): 3687–93. http://dx.doi.org/10.1039/c6sc05505b.

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The pyranose members of the pyrrolomorpholine spiroketal family have been synthesized by stereoselective spirocyclizations of a common glycal precursor, leading to the identification of novel 2-hydroxy analogues with more potent antioxidant activities than the natural products.
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27

Anderson, Oren P., Anthony GM Barrett, Jeremy J. Edmunds, et al. "Applications of crotyldiisopinocampheylboranes in synthesis: a formal total synthesis of (+)-calyculin A." Canadian Journal of Chemistry 79, no. 11 (2001): 1562–92. http://dx.doi.org/10.1139/v01-133.

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The formal total synthesis of the marine metabolite (+)-calyculin A is reported. The key steps involve (i) the use of Brown allylboration chemistry to control the relative and absolute stereochemistry of homoallylic alcohol arrays, thus setting eight of the desired stereocenters; (ii) Stille coupling methodology in the construction of the cyano tetraene unit of the natural product; and (iii) a modified Cornforth–Meyers approach to the synthesis of the oxazole fragment.Key words: calyculin, marine natural product, phosphatase inhibitor, total synthesis, palladium catalyzed coupling reactions, a
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28

Kambale, Digambar A., Sagar S. Thorat, Madhukar S. Pratapure, Rajesh G. Gonnade та Ravindar Kontham. "Lewis acid catalyzed cascade annulation of alkynols with α-ketoesters: a facile access to γ-spiroketal-γ-lactones". Chemical Communications 53, № 49 (2017): 6641–44. http://dx.doi.org/10.1039/c7cc03668j.

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A simple protocol for the synthesis of diverse unsaturated γ-spiroketal-γ-lactones has been developed by employing a Bi(OTf)<sub>3</sub> catalyzed cascade annulation of alkynols with α-ketoesters via a dual (π and σ) activation process.
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29

Gueyrard, David. "Extension of the Modified Julia Olefination on Carboxylic Acid Derivatives: Scope and Applications." Synlett 29, no. 01 (2017): 34–45. http://dx.doi.org/10.1055/s-0036-1590916.

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This account relates our work in the field of modified Julia olefination to extend this very useful olefination method to carboxylic acid derivatives. Since our preliminary results on lactones in 2005, the reaction has been extended to a large range of derivatives (lactams, imides and anhydrides) through an intra- or intermolecular process leading to a great variety of structures (enol ethers, enamides and exo enol esters). This article will also focus on the application of this methodology for the preparation of biologically interesting compounds and/or total syntheses of natural products suc
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30

L. Chang, Lydia, Charles G. Chavdarian, and Bruce C. Onisko. "Spiroketal Synthesis. Preparation of Functionalized 1,7-Dioxaspiro[5,5]undecanes." HETEROCYCLES 27, no. 3 (1988): 651. http://dx.doi.org/10.3987/com-87-4428.

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31

Mead, K., and B. Brewer. "Strategies in Spiroketal Synthesis Revisited: Recent Applications and Advances." Current Organic Chemistry 7, no. 3 (2003): 227–56. http://dx.doi.org/10.2174/1385272033372969.

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32

Yadav, J. S., and B. Muralidhar. "Stereoselective synthesis of spiroketal moiety of ionophore antibiotic routiennocin." Tetrahedron Letters 39, no. 18 (1998): 2867–68. http://dx.doi.org/10.1016/s0040-4039(98)00320-7.

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33

Quach, Rachelle, Daniel P. Furkert, and Margaret A. Brimble. "Total Synthesis of the Resorcyclic Acid Lactone Spiroketal Citreoviranol." Journal of Organic Chemistry 81, no. 18 (2016): 8343–50. http://dx.doi.org/10.1021/acs.joc.6b01503.

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34

Barrett, Anthony G. M., and Tony M. Raynham. "Approaches to avermectin assembly: Synthesis of the spiroketal system." Tetrahedron Letters 28, no. 46 (1987): 5615–18. http://dx.doi.org/10.1016/s0040-4039(00)96794-7.

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35

Trost, Barry M., and John A. Flygare. "A synthesis of the spiroketal subunit of (−)-calyculin A." Tetrahedron Letters 35, no. 24 (1994): 4059–62. http://dx.doi.org/10.1016/s0040-4039(00)73111-x.

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36

Yadav, J. S., Md Ataur Rahman, N. Mallikarjuna Reddy, and A. R. Prasad. "Synthesis of spiroketal fragment of ossamycin via Prins cyclization." Tetrahedron Letters 56, no. 2 (2015): 365–67. http://dx.doi.org/10.1016/j.tetlet.2014.11.097.

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37

Aponick, Aaron, and Jean Palmes. "Strategies for Spiroketal Synthesis Based on Transition-Metal Catalysis." Synthesis 44, no. 24 (2012): 3699–721. http://dx.doi.org/10.1055/s-0032-1317489.

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38

Lau, Cheuk Kun, Simon Crumpler, Kathy Macfarlane, Florence Lee, and Carl Berthelette. "Synthesis of AB and CD Spiroketal of Spongistatin 1." Synlett, no. 13 (2004): 2281–86. http://dx.doi.org/10.1055/s-2004-831334.

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39

Xue, Jijun, Hongrui Zhang, Tian Tian, et al. "Organohalogenite-Catalyzed Spiroketalization: Enantioselective Synthesis of Bisbenzannulated Spiroketal Cores." Advanced Synthesis & Catalysis 358, no. 3 (2016): 370–74. http://dx.doi.org/10.1002/adsc.201500390.

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40

Raji Reddy, Chada, Boinapally Srikanth, Uredi Dilipkumar, Kakita Veera Mohana Rao, and Bharatam Jagadeesh. "Total Synthesis of a 6,6-Spiroketal Metabolite, Dinemasone A." European Journal of Organic Chemistry 2013, no. 3 (2012): 525–32. http://dx.doi.org/10.1002/ejoc.201201246.

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41

Preuss, Rainer, Karl-Heinz Jung, and Richard R. Schmidt. "Spiroketal Synthesis. — A Case of Intramolecular Glycoside Bond Formation." Liebigs Annalen der Chemie 1992, no. 4 (1992): 377–82. http://dx.doi.org/10.1002/jlac.199219920166.

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42

Holoboski, Mark A., and Emil Koft. "Asymmetric synthesis of the milbemycin .beta.3 spiroketal subunit." Journal of Organic Chemistry 57, no. 3 (1992): 965–69. http://dx.doi.org/10.1021/jo00029a033.

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43

Sudo, Atsushi, Taichi Sano, Makoto Harada, and Dai Ishida. "Synthesis of Oligo(spiroketal)s from Naturally Occurringmyo-Inositol." ACS Macro Letters 3, no. 8 (2014): 808–12. http://dx.doi.org/10.1021/mz500353y.

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44

Wojtkielewicz, Agnieszka, Urszula Kiełczewska, and Jacek W. Morzycki. "Two-step Synthesis of Solasodine Pivalate from Diosgenin Pivalate." Molecules 24, no. 6 (2019): 1132. http://dx.doi.org/10.3390/molecules24061132.

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A two-step synthesis of solasodine pivalate from diosgenin pivalate is described. The key transformation involves the reaction of diosgenin pivalate with benzyl carbamate (CbzNH2) promoted by TMSOTf. During the reaction the F-ring of the spiroketal moiety opens up with a simultaneous introduction of a Cbz-protected amino group in position 26. A one-pot deprotection of 26-amine with AcBr/BuOH followed by the N-cyclization affords solasodine pivalate in 45% overall yield.
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45

Ireland, Robert E., Dieter Haebich, and Daniel W. Norbeck. "Convergent synthesis of polyether ionophore antibiotics: the synthesis of the monensin spiroketal." Journal of the American Chemical Society 107, no. 11 (1985): 3271–78. http://dx.doi.org/10.1021/ja00297a037.

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46

Smith, Amos B., R. Michael Corbett, George R. Pettit, et al. "Synthesis and biological evaluation of a spongistatin AB-spiroketal analogue." Bioorganic & Medicinal Chemistry Letters 12, no. 15 (2002): 2039–42. http://dx.doi.org/10.1016/s0960-894x(02)00305-0.

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47

Yadav, J. S., C. Nagendra Reddy, and G. Sabitha. "Synthesis of the C38–C54 spiroketal segment of halichondrin B." Tetrahedron Letters 53, no. 20 (2012): 2504–7. http://dx.doi.org/10.1016/j.tetlet.2012.02.090.

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48

Ardisson, J., J. P. Férézou, M. Julia, L. Lenglet, and A. Pancrazi. "Stereocontrolled synthesis of the spiroketal unit of 22,23-Dihydroavermectin B1b." Tetrahedron Letters 28, no. 18 (1987): 1997–2000. http://dx.doi.org/10.1016/s0040-4039(00)96029-5.

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49

Miyazawa, Masahiro, Toru Eizawa, Shoko Yoshihara, Akinori Hatanaka, Hajime Yokoyama, and Yoshiro Hirai. "Novel stereoselective synthesis of spiroketal structure using Pd(II)-catalyst." Tetrahedron Letters 55, no. 3 (2014): 753–56. http://dx.doi.org/10.1016/j.tetlet.2013.12.015.

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50

Drouet, Keith E., Taotao Ling, Hung V. Tran, and Emmanuel A. Theodorakis. "Enantioselective Synthesis of the [6,6] Spiroketal Core of Reveromycin A." Organic Letters 2, no. 2 (2000): 207–10. http://dx.doi.org/10.1021/ol991290v.

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