A new strategy for the synthesis of substituted dihydropyrones and tetrahydropyrones via palladium-catalyzed coupling of thioesters

被引：31

作者：

Fuwa, Haruhiko ^{[1
]}

Mizunuma, Kana ^{[1
]}

Matsukida, Seiji ^{[1
]}

Sasaki, Makoto ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Life Sci, Aoba Ku, Sendai, Miyagi 9808577, Japan

来源：

TETRAHEDRON | 2011年 / 67卷 / 27-28期

关键词：

Dihydropyrones; Tetrahydropyrones; Palladium-catalyzed coupling; Thioesters; Intramolecular oxa-conjugate cyclization; ENANTIOSELECTIVE TOTAL-SYNTHESIS; HETERO-MICHAEL ADDITION; STEREOSELECTIVE-SYNTHESIS; CONJUGATE ADDITION; GENE-CLUSTER; BETA-HYDROXYENONES; THIOL ESTERS; CONSTRUCTION; CONCISE; FRAGMENT;

D O I：

10.1016/j.tet.2011.03.114

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In this paper, we describe a new strategy for the synthesis of substituted dihydropyrones and tetrahydropyrones. By exploiting palladium-catalyzed coupling of thioesters with terminal alkynes or alkenylboronic acids, a variety of beta-hydroxy ynones or enones, respectively, could be prepared in an efficient manner under mild conditions. AgOTf-promoted intramolecular oxa-conjugate cyclization of beta-hydroxy ynones provided 2,6-substituted dihydropyrones in excellent yields. On the other hand, acid-catalyzed cyclization of beta-hydroxy enones caused racemization of the product 2,6-substituted tetrahydropyrones due to its reversible nature. Eventually, stereoselective hydrogenation of substituted dihydropyrones was found to be a solid and efficient approach for the synthesis of 2,6-cis-substituted tetrahydropyrone derivatives. (C) 2011 Elsevier Ltd. All rights reserved.

引用

页码：4995 / 5010

页数：16

共 68 条

[11] Strategies for the formation of tetrahydropyran rings in the synthesis of natural products [J].

Clarke, Paul A. ;

Santos, Soraia .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (09) :2045-2053

[12] Stereoselective construction of cis-2,6-disubstituted tetrahydropyrans via an intramolecular bismuth-mediated oxa-conjugate addition reaction [J].

Evans, PA ;

Andrews, WJ .

TETRAHEDRON LETTERS, 2005, 46 (34) :5625-5627

[13] Synthetic efforts toward the macrolactone core of leucascandrolide A [J].

Ferrie, Laurent ;

Boulard, Lucie ;

Pradaux, Fabienne ;

Bouzbouz, Sarnir ;

Reymond, Sbastien ;

Capdevielle, Patrice ;

Cossy, Janine .

JOURNAL OF ORGANIC CHEMISTRY, 2008, 73 (05) :1864-1880

[14] Toward the total synthesis of spirastrellolide A.: Part 1:: Strategic considerations and preparation of the southern domain [J].

Fuerstner, Alois ;

Fenster, Michael D. B. ;

Fasching, Bernhard ;

Godbout, Cedrickx ;

Radkowski, Karin .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (33) :5506-5510

[15]

Fukuyama T, 2004, ALDRICHIM ACTA, V37, P87

[16] Stereoselective synthesis of the AB-ring fragment of gambieric acid A [J].

Fuwa, Haruhiko ;

Suzuki, Akihiro ;

Sato, Kazushi ;

Sasaki, Makoto .

HETEROCYCLES, 2007, 72 :139-144

[17] Biosynthesis-Inspired Intramolecular Oxa-Conjugate Cyclization of α,β-Unsaturated Thioesters: Stereoselective Synthesis of 2,6-cis-Substituted Tetrahydropyrans [J].

Fuwa, Haruhiko ;

Noto, Kenkichi ;

Sasaki, Makoto .

ORGANIC LETTERS, 2011, 13 (07) :1820-1823

[18] Total Synthesis and Biological Assessment of (-)-Exiguolide and Analogues [J].

Fuwa, Haruhiko ;

Suzuki, Takaya ;

Kubo, Hiroshi ;

Yamori, Takao ;

Sasaki, Makoto .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (09) :2678-2688

[19] A CONCISE TOTAL SYTHESIS OF (±)-CENTROLOBINE [J].

Fuwa, Haruhiko ;

Noto, Kenkichi ;

Sasaki, Makoto .

HETEROCYCLES, 2010, 82 (01) :641-647

[20] An enantioselective total synthesis of aspergillides A and B [J].

Fuwa, Haruhiko ;

Yamaguchi, Hiroshi ;

Sasaki, Makoto .

TETRAHEDRON, 2010, 66 (38) :7492-7503

← 1 2 3 4 5 6 7 →