Stereodivergent syntheses of diospongins A and B

被引：0

作者：

Kote, Pamela ^{[1
]}

Holmgren III, John L. ^{[1
]}

Fruehauf, Erik C. ^{[1
]}

Ford, Hannah G. ^{[1
]}

Tate, Will M. ^{[1
]}

Scuderi, Michael A. ^{[1
]}

Quinn, Kevin J. ^{[1
]}

机构：

[1] Coll Holy Cross, Dept Chem, Worcester, MA 01610 USA

来源：

TETRAHEDRON | 2024年 / 166卷

关键词：

Natural products; Total synthesis; diospongin; Olefin metathesis; Oxa-Michael addition; One-pot reactions; ASYMMETRIC TOTAL SYNTHESES; STEREOSELECTIVE-SYNTHESIS; TETRAHYDROPYRAN-4-ONES; (+/-)-DIOSPONGIN; FRAGMENT;

D O I：

10.1016/j.tet.2024.134209

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Syntheses of the tetrahydropyranol natural products (+/-)-diospongin A and (+/-)-diospongin B, in four steps (37 % overall) and seven (14 % overall) or nine steps (25 % overall) respectively, are reported. A common homoallylic alcohol serves as a key intermediate for stereodivergent, one-pot olefin metathesis/deprotection/oxa-Michael cyclization steps that establish the requisite 2,6-stereochemical relationships of the diastereomeric targets. Cross metathesis results in formation of an acyclic, unsaturated ketone that undergoes conjugate addition to give diospongin A directly. Ring-closing metathesis/conjugate addition provides a diastereomerically pure bicyclic lactone, possessing the contra-thermodynamic 2,6-trans stereochemistry, that can be converted to diospongin B in either two or four steps.

引用

页数：7

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