Asymmetric epoxidation of cis-alkenes with arabinose-derived ketones: enantioselective synthesis of the side chain of Taxol®

Tony K.M. Shing; To Luk; Chi M. Lee

doi:10.1016/j.tet.2006.01.116

Asymmetric epoxidation of cis-alkenes with arabinose-derived ketones: enantioselective synthesis of the side chain of Taxol^®

Tony K.M. Shing, To Luk, Chi M. Lee

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

Abstract

The ee values of asymmetric epoxidation of cis-ethyl cinnamate 15 with arabinose-derived ketones as catalyst and Oxone^® as the terminal oxidant were found to increase inversely with the size of the catalyst acetal blocking group. Ketone catalyst 2, with the least bulky methoxy acetal group, displayed the best enantioselectivity and afforded ethyl (2R,3R)-3-phenylglycidate 16 in 68% ee. Epoxide 16 was readily converted into a protected side chain of Taxol^® in five steps with an overall yield of 89%. The enantioselectivity of the epoxidation of other cis-alkenes was moderate to poor.

Original language	English
Pages (from-to)	6621-6629
Number of pages	9
Journal	Tetrahedron
Volume	62
Issue number	28
DOIs	https://doi.org/10.1016/j.tet.2006.01.116
Publication status	Published - 2006 Jul 10
Externally published	Yes

Keywords

Asymmetric synthesis
Dioxirane
Epoxidation

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Access to Document

10.1016/j.tet.2006.01.116

Cite this

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title = "Asymmetric epoxidation of cis-alkenes with arabinose-derived ketones: enantioselective synthesis of the side chain of Taxol{\textregistered}",

abstract = "The ee values of asymmetric epoxidation of cis-ethyl cinnamate 15 with arabinose-derived ketones as catalyst and Oxone{\textregistered} as the terminal oxidant were found to increase inversely with the size of the catalyst acetal blocking group. Ketone catalyst 2, with the least bulky methoxy acetal group, displayed the best enantioselectivity and afforded ethyl (2R,3R)-3-phenylglycidate 16 in 68% ee. Epoxide 16 was readily converted into a protected side chain of Taxol{\textregistered} in five steps with an overall yield of 89%. The enantioselectivity of the epoxidation of other cis-alkenes was moderate to poor.",

keywords = "Asymmetric synthesis, Dioxirane, Epoxidation",

author = "Shing, {Tony K.M.} and To Luk and Lee, {Chi M.}",

note = "Funding Information: This research was supported by a CUHK Direct Grant. ",

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T1 - Asymmetric epoxidation of cis-alkenes with arabinose-derived ketones

T2 - enantioselective synthesis of the side chain of Taxol®

AU - Shing, Tony K.M.

AU - Luk, To

AU - Lee, Chi M.

N1 - Funding Information: This research was supported by a CUHK Direct Grant.

PY - 2006/7/10

Y1 - 2006/7/10

N2 - The ee values of asymmetric epoxidation of cis-ethyl cinnamate 15 with arabinose-derived ketones as catalyst and Oxone® as the terminal oxidant were found to increase inversely with the size of the catalyst acetal blocking group. Ketone catalyst 2, with the least bulky methoxy acetal group, displayed the best enantioselectivity and afforded ethyl (2R,3R)-3-phenylglycidate 16 in 68% ee. Epoxide 16 was readily converted into a protected side chain of Taxol® in five steps with an overall yield of 89%. The enantioselectivity of the epoxidation of other cis-alkenes was moderate to poor.

AB - The ee values of asymmetric epoxidation of cis-ethyl cinnamate 15 with arabinose-derived ketones as catalyst and Oxone® as the terminal oxidant were found to increase inversely with the size of the catalyst acetal blocking group. Ketone catalyst 2, with the least bulky methoxy acetal group, displayed the best enantioselectivity and afforded ethyl (2R,3R)-3-phenylglycidate 16 in 68% ee. Epoxide 16 was readily converted into a protected side chain of Taxol® in five steps with an overall yield of 89%. The enantioselectivity of the epoxidation of other cis-alkenes was moderate to poor.

KW - Asymmetric synthesis

KW - Dioxirane

KW - Epoxidation

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