Stereospecific intramolecular Michael addition to (-)-carvone based on temporary sulfur connection

被引：16

作者：

Bachi, MD ^{[1
]}

Bilokin, YV ^{[1
]}

Melman, A ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel

来源：

TETRAHEDRON LETTERS | 1998年 / 39卷 / 19期

基金：

以色列科学基金会;

关键词：

elimination reactions; enantioselection; Michael reactions; terpenes and terpenoids;

D O I：

10.1016/S0040-4039(98)00327-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An acetic acid residue (CH2CO2Me) was stereoselectively attached to (-)-carvone (7) to give (1R,2S,5R)-(5-isopropenyl-2-methyl-3-oxocyclohexyl)acetic acid methyl ester (21) in a process involving the following stages: i) addition of ClSCH2CO2Me to the isopropenyl group of 7 to give, after oxidation, [1-chloro-2(RS)-(1(R),4-methyl-5-oxocyclohex-3-enyl)propane-2-sulfonyl] acetic acid methyl ester (18); ii) intramolecular Michael addition of 18 to afford (1S,2S,4(RS),5R,8S)-4-chloromethyl-4,8-dimethyl-3,3,7-trioxo-3-thiabicyclo [3.3.1]nonane-2-carboxylic acid methyl ester (20); iii) disconnection of the acetic acid moiety by a tandem reductive elimination involving sulfur extrusion and restoration of the isopropenyl group (20 --> 21). (C) 1998 Elsevier Science Ltd. All rights reserved.

引用

页码：3035 / 3038

页数：4

共 19 条

[1] Stereoselective synthesis of (+/-)-alpha-kainic acid using free radical key reactions [J].

Bachi, MD ;

BarNer, N ;

Melman, A .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (20) :7116-7124

[2]

Bachi MD, 1996, SYNLETT, P60

[3] Enantioselective total synthesis of (-)-alpha-kainic acid through free radical cyclization of an alkenyl monothioformimide [J].

Bachi, MD ;

Melman, A .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (06) :1896-1898

[4] SILICON-TETHERED REACTIONS [J].

BOLS, M ;

SKRYDSTRUP, T .

CHEMICAL REVIEWS, 1995, 95 (05) :1253-1277

[5]

Fensterbank L, 1997, SYNTHESIS-STUTTGART, P813

[6] Stereochemical control in organic synthesis using silicon-containing compounds [J].

Fleming, I ;

Barbero, A ;

Walter, D .

CHEMICAL REVIEWS, 1997, 97 (06) :2063-2192

[7] A SHORT SYNTHESIS OF (+/-)-CUPARENE [J].

ISHIBASHI, H ;

SO, TS ;

NAKATANI, H ;

MINAMI, K ;

IKEDA, M .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (12) :827-828

[8]

Koval I. V., 1995, Russ. Chem. Rev, V64, P731, DOI [DOI 10.1070/RC1995V064N08ABEH000172, 10.1070/rc1995v064n08abeh000172]

[9]

Kuhle E., 1973, CHEM SULFENIC ACIDS

[10] A THIOXANONE-BASED CHIRAL TEMPLATE - ASYMMETRIC INDUCTION IN THE [2,3]-SIGMATROPIC REARRANGEMENT OF SULFUR YLIDS - ENANTIOSELECTIVE PREPARATION OF C-BETA-CHIRAL PENT-4-ENOIC ACIDS [J].

KURTH, MJ ;

TAHIR, SH ;

OLMSTEAD, MM .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (08) :2286-2288

← 1 2 →