An 鈥淎protic鈥?Tamao Oxidation/Syn-Selective Tautomerization Reaction for the Efficient Synthesis of the C(1)鈥揅(9) Fragment of Fludelone
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- 作者：Tyler J. Harrison ; Philippe M. A. Rabbat ; James L. Leighton
- 刊名：Organic Letters
- 出版年：2012
- 出版时间：September 21, 2012
- 年：2012
- 卷：14
- 期：18
- 页码：4890-4893
- 全文大小：294K
- 年卷期：v.14,no.18(September 21, 2012)
- ISSN：1523-7052
文摘
An efficient synthesis of the C(1)鈥揅(9) fragment of fludelone has been developed. The key step is a tandem silylformylation鈥揷rotylsilylation/Tamao oxidation sequence that establishes the C(5) ketone, the C(6), C(7), and C(8) stereocenters, and the C(9) alkene in a single operation from a readily accessed starting material. The stereochemical outcome at C(6) depends critically on the development of an 鈥渁protic鈥?Tamao oxidation, which leads to a reversal in the intrinsic diastereoselectivity observed using 鈥渟tandard鈥?Tamao oxidation conditions.