Racemization in prins cyclization reactions

被引：105

作者：

Jasti, Ramesh ^{[1
]}

Rychnovsky, Scott D. ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 41期

关键词：

D O I：

10.1021/ja064783l

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Isotopic labeling experiments were performed to elucidate a new mechanism for racemization in Prins cyclization reactions. The loss in optical activity for these reactions was shown to occur by 2-oxonia-Cope rearrangements by way of a (Z)-oxocarbenium ion intermediate. Reaction conditions such as solvent, temperature, and the nucleophile employed played a critical role in whether an erosion in enantiomeric excess was observed. Additionally, certain structural features of Prins cyclization precursors were also shown to be important for preserving optical purity in these reactions.

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页码：13640 / 13648

页数：9

相关论文

共 67 条

[1]

ADAMS DR, 1977, SYNTHESIS-STUTTGART, P661

[2] Aromatic 4-tetrahydropyranyl and 4-quinuclidinyl cations. Linking prins with Cope and Grob [J].

Alder, RW ;

Harvey, JN ;

Oakley, MT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (18) :4960-4961

[3] THE OLEFIN ALDEHYDE CONDENSATION - THE PRINS REACTION [J].

ARUNDALE, E ;

MIKESKA, LA .

CHEMICAL REVIEWS, 1952, 51 (03) :505-555

[4] Total synthesis of (+)-dactylolide through an efficient sequential peterson olefination and prins cyclization reaction [J].

Aubele, DL ;

Wan, SY ;

Floreancig, PE .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (22) :3485-3488

[5] Rapid stereocontrolled assembly of the fully substituted C-aryl glycoside of kendomycin with a Prins cyclization:: a formal synthesis [J].

Bahnck, Kevin B. ;

Rychnovsky, Scott D. .

CHEMICAL COMMUNICATIONS, 2006, (22) :2388-2390

[6] Total synthesis of a diastereomer of the marine natural product clavosolide A [J].

Barry, CS ;

Bushby, N ;

Charmant, JPH ;

Elsworth, JD ;

Harding, JR ;

Willis, CL .

CHEMICAL COMMUNICATIONS, 2005, (40) :5097-5099

[7] Probing the mechanism of Prins cyclisations and application to the synthesis of 4-hydroxytetrahydropyrans [J].

Barry, CS ;

Bushby, N ;

Harding, JR ;

Hughes, RA ;

Parker, GD ;

Roe, R ;

Willis, CL .

CHEMICAL COMMUNICATIONS, 2005, (29) :3727-3729

[8] Stereoselective synthesis of 4-hydroxy-2,3,6-trisubstituted tetrahydropyrans [J].

Barry, CSJ ;

Crosby, SR ;

Harding, JR ;

Hughes, RA ;

King, CD ;

Parker, GD ;

Willis, CL .

ORGANIC LETTERS, 2003, 5 (14) :2429-2432

[9] Tetrahydropyran rings from a Mukaiyama-Michael cascade reaction [J].

Bolla, ML ;

Patterson, B ;

Rychnovsky, SD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (46) :16044-16045

[10] PREPARATION OF ENANTIOENRICHED TETRAHYDROPYRIDINES BY IMINIUM ION-VINYLSILANE CYCLIZATIONS [J].

CASTRO, P ;

OVERMAN, LE ;

ZHANG, XM ;

MARIANO, PS .

TETRAHEDRON LETTERS, 1993, 34 (33) :5243-5246

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