Asymmetric Total Syntheses of (−)-Hedycoropyrans A and B

The first and asymmetric total synthesis of (−)-hedycoropyrans A (1) was accomplished in 18 steps with 5.4% overall yield. The key features of our strategy include (1) construction of the unusual trans-2-aryl-6-alkyl tetrahydropyran core via Achmatowicz rearrangement, Zn-mediated reductive deoxygena...

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Bibliographic Details
Published in:Journal of organic chemistry 2017-01, Vol.82 (2), p.1127-1135
Main Authors: Li, Zhilong, Tong, Rongbiao
Format: Article
Language:English
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Summary:The first and asymmetric total synthesis of (−)-hedycoropyrans A (1) was accomplished in 18 steps with 5.4% overall yield. The key features of our strategy include (1) construction of the unusual trans-2-aryl-6-alkyl tetrahydropyran core via Achmatowicz rearrangement, Zn-mediated reductive deoxygenation, and Heck–Matsuda coupling reaction, and (2) installation of 3,4-anti-dihydroxy from the corresponding 3,4-syn-dihydroxy THP through chemo- and regioselective IBX oxidation and Evans–Saksena reduction. In addition, C2 epimerization of (−)-hedycoropyan A (1) under the acidic condition furnished (−)-hedycoropyan B (2) with 71% yield. This finding might suggest the biogenetic origin of hedycoropyran B.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.6b02738