Total Synthesis of (+)-Phorboxazole A Exploiting the Petasis−Ferrier Rearrangement

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71

作者:

AmosB.SmithIIIKevinP.MinbiolePatrickR.Verhoest

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摘要:

A highly convergent, stereocontrolled total synthesis of the potent antiproliferative agent (+)-phorboxazole A (1) has been achieved. Highlights of the synthesis include:  modified Petasis−Ferrier rearrangements for assembly of both the C(11−15) and C(22−26) cis-tetrahydropyran rings; extension of the Julia olefination to the synthesis of enol ethers; the design, synthesis, and application of a novel bifunctional oxazole linchpin; and Stille coupling of a C(28) trimethyl stannane with a C(29) oxazole triflate. The longest linear sequence leading to (+)-phorboxazole A (1) was 27 steps, with an overall yield of 3%.

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DOI:

10.1021/ja011604l

被引量:

485

年份:

2001

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2003
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