A peculiar transition-metal-free cyclodimerization of propargylic alcohols to vinyl bicyclic ketals

被引：13

作者：

Trofimov, Boris A. ^{[1
]}

Schmidt, Elena Yu. ^{[1
]}

Bidusenko, Ivan A. ^{[1
]}

Ushakov, Igor' A. ^{[1
]}

Protsuk, Nadezhda I. ^{[1
]}

Zorina, Nadezhda V. ^{[1
]}

Mikhaleva, Albina I. ^{[1
]}

机构：

[1] Russian Acad Sci, Siberian Branch, AE Favorsky Irkutsk Inst Chem, Irkutsk 664033, Russia

来源：

TETRAHEDRON | 2012年 / 68卷 / 04期

基金：

俄罗斯基础研究基金会;

关键词：

Acetylene; Acetylenic alcohols; 6,8-Dioxabicyclo[3.2.1]octanes; Super base; ENANTIOSELECTIVE ADDITION; STEREOSELECTIVE-SYNTHESIS; NUCLEOPHILIC-ADDITION; ASYMMETRIC-SYNTHESIS; TERTIARY ALCOHOLS; C-C; KETONES; ACETOPHENONE; CONSTRUCTION; MUSTH;

D O I：

10.1016/j.tet.2011.11.050

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Propargylic alcohols, alkylaryl(hetaryl)ethynyl carbinols, under transition-metal-free conditions (KOH/DMSO, 70-80 degrees C, 10-15 min) unexpectedly undergo stereoselective cyclodimerization to 7-methylene-6,8-dioxabicyclo[3.2.1]octanes having the scaffold of known insect pheromones and marine toxins. Under acetylenic pressure the yields of bicyclic ketals reach 80%. In all the cases, the cyclodimers are formed exclusively as one diastereomer. (C) 2011 Elsevier Ltd. All rights reserved.

引用

页码：1241 / 1246

页数：6

共 28 条

[1] TiCl4 catalyzed tandem construction of C-C and C-O bonds:: a simple and one-pot atom-economical stereoselective synthesis of spiro-oxindoles [J].

Basavaiah, D ;

Rao, JS ;

Reddy, RJ ;

Rao, AJ .

CHEMICAL COMMUNICATIONS, 2005, (20) :2621-2623

[2] A convenient route to condensed-ring aromatic acetylenes [J].

Crisp, GT ;

Jiang, YL .

SYNTHETIC COMMUNICATIONS, 1998, 28 (14) :2571-2576

[3] Human risk associated with palytoxin exposure [J].

Deeds, Jonathan R. ;

Schwartz, Michael D. .

TOXICON, 2010, 56 (02) :150-162

[4]

Favorskii A.E., 1906, ZH ROSS KHIM OBSHCH, V37, P643

[5] Recent progress in the catalytic synthesis of tertiary alcohols from ketones with organometallic reagents [J].

Hatano, Manabu ;

Ishihara, Kazuaki .

SYNTHESIS-STUTTGART, 2008, (11) :1647-1675

[6] Direct propargylic substitution of hydroxyl group in propargylic alcohols [J].

Kabalka, George W. ;

Yao, Min-Liang .

CURRENT ORGANIC SYNTHESIS, 2008, 5 (01) :28-32

[7] The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water [J].

Li, Chao-Jun .

ACCOUNTS OF CHEMICAL RESEARCH, 2010, 43 (04) :581-590

[8] Studies toward the total synthesis of cyclodidemniserinol trisulfate. Part I: 3,5,7-Trisubstituted 6,8-dioxabicyclo [3.2.1] octane core structure construction via a convergent and a linear stereoselective synthesis [J].

Liu, Jian-Hua ;

Song, Lai-Dong ;

Long, Ya-Qiu .

TETRAHEDRON LETTERS, 2009, 50 (32) :4587-4591

[9] ORGANOMETALLIC CHEMISTRY IN INDUSTRIAL VITAMIN-A AND VITAMIN-E SYNTHESIS [J].

MERCIER, C ;

CHABARDES, P .

PURE AND APPLIED CHEMISTRY, 1994, 66 (07) :1509-1518

[10] Pheromone synthesis [J].

Mori, K .

CHEMISTRY OF PHEROMONES AND OTHER SEMIOCHEMICALS I, 2004, 239 :1-50

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