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(c) See ref 2.
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26444511837
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note
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See the Supporting Information for method of preparation. Note that compounds 7-11 in Scheme 1 were prepared as an inconsequential mixture of acetonide diastereomers so that rac-5 could serve as starting material.
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13
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Representative examples of its use in synthesis: (c) Boeckman, R. K., Jr.; Yoon, S. K.; Heckendorn, D. K. J. Am. Chem. Soc. 1991, 113, 9682-9684.
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(a) Kagan, H. B. Tetrahedron 2003, 59, 10351-10372.
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For cyclopropanation of secondary α-hydroxy, α-alkoxy, and α-amino ester substrates, respectively, see: (a) Cho, S. Y.; Cha, J. K. Org. Lett. 2000, 2, 1337-1340.
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0002561992
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Alternative methods involve Sharpless asymmetric epoxidation and asymmetric dihydroxylation of the cyclopropylidene group, followed by ring expansion. Unfortunately, an allylic hydroxyl group is a requirement for high enantioselectivity in the epoxidation event, and the cinchona-catalyzed asymmetric dihydroxylation of a tetrasubstituted cyclopropylidene olefin proceeds with only modest selectivity. For details, see: (a) Nemoto, H.; Fukumoto, K. Synlett 1997, 863-875.
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For a related study, see: (c) Youn, J.-H.; Lee, J.; Cha, J. K. Org. Lett. 2001, 3, 2935-2938.
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26444548816
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Racemic 11 had previously been prepared by the spiroannulation method of Trost from the corresponding methyl ketone. For details, see: Thomas W. Lee, Ph.D. Thesis, Harvard University, 2001.
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Lee, T.W.1
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26444445873
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note
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For a review on other synthetic approaches to dolabellanes, see ref 4.
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