Highly Stereoselective Diels-Alder Reactions Catalyzed by Diboronate Complexes

被引：0

作者：

Li, Yuan-He ^{[1
,2
,3
]}

Zhang, Su-Lei ^{[1
,2
,3
]}

Lu, Yong ^{[1
,2
,3
]}

Xiao, Bo ^{[4
]}

Sun, Tian-Yu ^{[4
]}

Xu, Qian-Qian ^{[1
,2
,3
]}

Chen, Jia-Hua ^{[1
,2
,3
]}

Yang, Zhen ^{[1
,2
,3
,5
,6
]}

机构：

[1] Peking Univ, Minist Educ, Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China

[2] Peking Univ, Beijing Natl Lab Mol Sci BNLMS, Beijing 100871, Peoples R China

[3] Peking Univ, Peking Tsinghua Ctr Life Sci, Beijing 100871, Peoples R China

[4] Peking Univ, Shenzhen Grad Sch, State Key Lab Chem Oncogen, Lab Computat Chem & Drug Design, Shenzhen 518055, Peoples R China

[5] Shenzhen Bay Lab, Shenzhen 518055, Peoples R China

[6] Peking Univ, Shenzhen Grad Sch, State Key Lab Chem Oncogen, Key Lab Chem Genom, Shenzhen 518055, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 33期

基金：

美国国家科学基金会;

关键词：

Asymmetric Catalysis; Bispyrrolidine Diboronates; Diels-Alder Reaction; Exo-Selectivity; Pericyclic Reaction; ASYMMETRIC TOTAL-SYNTHESIS; CYCLOADDITION REACTIONS; CHIRAL CATALYSTS; EXO-SELECTIVITY; DESIGN; ACIDS; DIENOPHILES;

D O I：

10.1002/anie.202303075

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A highly enantioselective catalytic system for exo-Diels-Alder reactions was developed based on the newly discovered bispyrrolidine diboronates (BPDB). Activated by various Lewis or Bronsted acids, BPDB can catalyze highly stereoselective asymmetric exo-Diels-Alder reactions of monocarbonyl-based dienophiles. When 1,2-dicarbonyl-based dienophiles are used, the catalyst can sterically distinguish between the two binding sites, which leads to highly regioselective asymmetric Diels-Alder reactions. BPDB can be prepared as crystalline solids on a large scale and are stable under ambient condition. Single-crystal X-ray analysis of the structure for acid-activated BPDB indicated that its activation involves cleavage of a labile B & LARR;N bond.

引用

页数：7

共 56 条

[1] Acylammonium Salts as Dienophiles in Diels-Alder/Lactonization Organocascades [J].

Abbasov, Mikail E. ;

Hudson, Brandi M. ;

Tantillo, Dean J. ;

Romo, Daniel .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (12) :4492-4495

[2] Toward reliable density functional methods without adjustable parameters: The PBE0 model [J].

Adamo, C ;

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6158-6170

[3] Examinations into the process of diene synthesis. [J].

Alder, K ;

Stein, G .

ANGEWANDTE CHEMIE, 1937, 50 :0510-0519

[4] Enantioselective Catalysis Based on Cationic Oxazaborolidines [J].

Corey, E. J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (12) :2100-2117

[5]

Corey EJ, 2002, ANGEW CHEM INT EDIT, V41, P1650, DOI 10.1002/1521-3773(20020517)41:10<1650::AID-ANIE1650>3.0.CO

[6]

2-B

[7] 1ST APPLICATION OF ATTRACTIVE INTRAMOLECULAR INTERACTIONS TO THE DESIGN OF CHIRAL CATALYSTS FOR HIGHLY ENANTIOSELECTIVE DIELS-ALDER REACTIONS [J].

COREY, EJ ;

LOH, TP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (23) :8966-8967

[8] Asymmetric Diels-Alder reactions catalyzed by a triflic acid activated chiral oxazaborolidine [J].

Corey, EJ ;

Shibata, T ;

Lee, TW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (15) :3808-3809

[9] USE OF TRANS-METHYL BETA-NITROACRYLATE IN DIELS-ALDER REACTIONS [J].

DANISHEFSKY, S ;

PRISBYLLA, MP ;

HINER, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (09) :2918-2920

[10]

Diels O, 1928, LIEBIGS ANN CHEM, V460, P98

← 1 2 3 4 5 6 →