An asymmetric route to novel chiral cyclohexenones with spiro-connected cyclopentenes. Further utility of chiral bicyclic thiolactams and the [3,3] thio-Claisen products

被引：29

作者：

Lemieux, RM ^{[1
]}

Devine, PN ^{[1
]}

Mechelke, MF ^{[1
]}

Meyers, AI ^{[1
]}

机构：

[1] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1999年 / 64卷 / 10期

关键词：

D O I：

10.1021/jo982426q

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Sequential allylation of chiral, nonracemic thiolactam 8 affords clean thio-Claisen [3,3] products ii. The stereoselectivity of the rearrangement was found to be on the order of 10-11:1, with the exo-endo products responsible for the mixture. Addition of hydride or methyllithium-cerium chloride gave clean addition to the thiolactam in the form of its iminium salts 12. Hydrolysis gave 4,4-dialkylcyclohexenones 16, which were cyclized to the cyclopentene derivatives 16 using Grubbs' catalyst.

引用

页码：3585 / 3591

页数：7

共 16 条

[1]

Armstrong SK, 1998, J CHEM SOC PERK T 1, P371

[2]

COUTURIER JL, 1993, ANGEW CHEM INT EDIT, V32, P112, DOI 10.1002/anie.199301121

[3] THIO-CLAISEN REARRANGEMENTS - AN ASYMMETRIC-SYNTHESIS OF 4,4-DISUBSTITUTED CYCLOHEXENONES WITH VICINAL QUATERNARY AND TERTIARY STEREOCENTERS [J].

DEVINE, PN ;

MEYERS, AI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (06) :2633-2634

[4] Recent advances in olefin metathesis and its application in organic synthesis [J].

Grubbs, RH ;

Chang, S .

TETRAHEDRON, 1998, 54 (18) :4413-4450

[5] FACILE REGIOSELECTIVE FORMATION OF THIOPEPTIDE LINKAGES FROM OLIGOPEPTIDES WITH NEW THIONATION REAGENTS [J].

LAJOIE, G ;

LEPINE, F ;

MAZIAK, L ;

BELLEAU, B .

TETRAHEDRON LETTERS, 1983, 24 (36) :3815-3818

[6] Asymmetric synthesis of (-)-trichodiene. Generation of vicinal stereogenic quaternary centers via the thio-Claisen rearrangement [J].

Lemieux, RM ;

Meyers, AI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (22) :5453-5457

[7]

LEMIEUX RM, 1998, UNPUB J ORG CHEM

[8]

Meyers AI, 1997, B SOC CHIM FR, V134, P283

[9] AN ASYMMETRIC-SYNTHESIS OF 4,4-DIALKYLCYCLOHEXENONES AND 6,6-DIALKYLCYCLOHEXENONES AND 4,4-DIALKYLCYCLOPENTENONES AND 5,5-DIALKYLCYCLOPENTENONES - APPLICATION TO THE TOTAL SYNTHESIS OF (-)-SILPHIPERFOL-6-ENE [J].

MEYERS, AI ;

LEFKER, BA .

TETRAHEDRON, 1987, 43 (23) :5663-5676

[10] SYNTHESES AND ACTIVITIES OF NEW SINGLE-COMPONENT, RUTHENIUM-BASED OLEFIN METATHESIS CATALYSTS [J].

NGUYEN, ST ;

GRUBBS, RH ;

ZILLER, JW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (21) :9858-9859

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