Enantio- and Diastereoselective Access to Distant Stereocenters Embedded within Tetrahydroxanthenes: Utilizing ortho-Quinone Methides as Reactive Intermediates in Asymmetric Bronsted Acid Catalysis

被引：208

作者：

Hsiao, Chien-Chi ^{[1
]}

Liao, Hsuan-Hung ^{[1
]}

Rueping, Magnus ^{[1
]}

机构：

[1] Rhein Westfal TH Aachen, Inst Organ Chem, D-52074 Aachen, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 48期

关键词：

cyclization; enantioselectivity; heterocycles; organocatalysis; synthetic methods; DIELS-ALDER REACTION; ENANTIOSELECTIVE SYNTHESIS; NATURAL-PRODUCTS; ONE-POT; 1,4-ASYMMETRIC INDUCTION; NAZAROV CYCLIZATION; DESYMMETRIZATION; ACTIVATION; DERIVATIVES; ION;

D O I：

10.1002/anie.201406587

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A protocol for the highly enantioselective synthesis of 9-substituted tetrahydroxanthenones by means of asymmetric Bronsted acid catalysis has been developed. A chiral binol-based N-triflyphosphoramide was found to promote the in situ generation of ortho-quinone methides and their subsequent reaction with 1,3-cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio-and diastereoselective Bronsted acid catalyzed desymmetrization of 5-monosubstituted 1,3-dicarbonyl substrates with ortho-quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.

引用

页码：13258 / 13263

页数：6

共 106 条

[1] Stronger bronsted acids [J].

Akiyama, Takahiko .

CHEMICAL REVIEWS, 2007, 107 (12) :5744-5758

[2] Asymmetric Cycloadditions of o-Quinone Methides Employing Chiral Ammonium Fluoride Precatalysts [J].

Alden-Danforth, Ethan ;

Scerba, Michael T. ;

Lectka, Thomas .

ORGANIC LETTERS, 2008, 10 (21) :4951-4953

[3]

[Anonymous], 2014, ANGEW CHEM-GER EDIT

[4] Generation of ortho-Quinone Methides by p-TsOH on Silica and Their Hetero-Diels-Alder Reactions with Styrenes [J].

Batsomboon, Paratchata ;

Phakhodee, Wong ;

Ruchirawat, Somsak ;

Ploypradith, Poonsakdi .

JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (10) :4009-4012

[5] Biosynthetic and biomimetic electrocyclizations [J].

Beaudry, CM ;

Malerich, JP ;

Trauner, D .

CHEMICAL REVIEWS, 2005, 105 (12) :4757-4778

[6] A Concise Synthesis of Berkelic Acid Inspired by Combining the Natural Products Spicifernin and Pulvilloric Acid [J].

Bender, Christopher F. ;

Yoshimoto, Francis K. ;

Paradise, Christopher L. ;

De Brabander, Jef K. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (32) :11350-+

[7] Mechanistic investigations of the acid-catalyzed cyclization of a vinyl ortho-quinone methide [J].

Bishop, Lee M. ;

Winkler, Michael ;

Houk, Kendall N. ;

Bergman, Robert G. ;

Trauner, Dirk .

CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (18) :5405-5408

[8] Photoactivation of amino-substituted 1,4-benzoquinones for release of carboxylate and phenolate leaving groups using visible light [J].

Chen, Yugang ;

Steinmetz, Mark G. .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (16) :6053-6060

[9] Ultra-remote stereocontrol by conformational communication of information along a carbon chain [J].

Clayden, J ;

Lund, A ;

Vallverdú, LS ;

Helliwell, M .

NATURE, 2004, 431 (7011) :966-971

[10] Helix Persistence and Breakdown in Oligoureas of Metaphenylenediamine: Apparent Diastereotopicity as a Spectroscopic Marker of Helix Length in Solution [J].

Clayden, Jonathan ;

Lemiegre, Loiec ;

Morris, Gareth A. ;

Pickworth, Mark ;

Snape, Timothy J. ;

Jones, Lyn H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (45) :15193-15202

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