A Tandem Iridium-Catalyzed "Chain-Walking"/Cope Rearrangement Sequence

被引：30

作者：

Sommer, Heiko ^{[1
]}

Weissbrod, Tal ^{[1
]}

Marek, Ilan ^{[1
]}

机构：

[1] Technion Israel Inst Technol, Schulich Fac Chem, IL-32000 Haifa, Israel

来源：

ACS CATALYSIS | 2019年 / 9卷 / 03期

基金：

欧盟地平线“2020”; 欧洲研究理事会;

关键词：

chain-walking remote functionalization; iridium catalysis; Cope rearrangement; alkenyl cyclopropane; C-H FUNCTIONALIZATION; ALKENE ISOMERIZATION-HYDROBORATION; REMOTE FUNCTIONALIZATION; STEREOSELECTIVE PREPARATION; ENANTIOSELECTIVE SYNTHESIS; CYCLOPROPENE DERIVATIVES; TREMULANE SKELETON; ENOL ETHERS; COMPLEX; CONSTRUCTION;

D O I：

10.1021/acscatal.9b00118

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

An iridium-catalyzed tandem olefin migration/Cope rearrangement of alkenyl omega-ene cyclopropanes is reported. By this means, a variety of complex annulenes are obtained as single diastereomers starting from cyclopropyl ester derived from simple 1,omega-dienes and alkenyldiazo compounds. Long-range olefin migration over up to 10 positions could be realized and coupled with an efficient Cope rearrangement to yield valuable scaffolds. Various functional groups are well-tolerated, giving rise to densely functionalized products. Furthermore, the present methodology could be successfully extended to yield bicyclic cycloheptenones starting from readily available alkenyl cyclopropanols via a Kulinkovich reaction.

引用

页码：2400 / 2406

页数：13

共 67 条

[1] ISOMERIZATION OF ALLYL ETHERS CATALYZED BY CATIONIC IRIDIUM COMPLEX [IR(CYCLO-OCTA-1,5-DIENE)(PMEPH2)2]PF6 - HIGHLY STEREOSELECTIVE ROUTE TO TRANS-PROPENYL ETHERS [J].

BAUDRY, D ;

EPHRITIKHINE, M ;

FELKIN, H .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1978, (16) :694-695

[2] Mechanistic Understanding of Transition-Metal-Catalyzed Olefin Isomerization: Metal-Hydride Insertion-Elimination vs. π-Allyl Pathways [J].

Biswas, Soumik .

COMMENTS ON INORGANIC CHEMISTRY, 2015, 35 (06) :301-331

[3] BIOMIMETIC CONTROL OF CHEMICAL SELECTIVITY [J].

BRESLOW, R .

ACCOUNTS OF CHEMICAL RESEARCH, 1980, 13 (06) :170-177

[4] Innate and Guided C-H Functionalization Logic [J].

Brueckl, Tobias ;

Baxter, Ryan D. ;

Ishihara, Yoshihiro ;

Baran, Phil S. .

ACCOUNTS OF CHEMICAL RESEARCH, 2012, 45 (06) :826-839

[5] Thermal, catalytic, regiospecific functionalization of alkanes [J].

Chen, HY ;

Schlecht, S ;

Semple, TC ;

Hartwig, JF .

SCIENCE, 2000, 287 (5460) :1995-1997

[6] Unsaturated fatty alcohol derivatives as a source of substituted allylzirconocene [J].

Chinkov, N ;

Levin, A ;

Marek, I .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (03) :465-468

[7] Stereoselective preparation of dienyl zirconocene complexes via a tandem allylic C-H bond activation-elimination sequence [J].

Chinkov, N ;

Majumdar, S ;

Marek, I .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (43) :13258-13264

[8] New approach to the stereoselective synthesis of metalated dienes via an isomerization-elimination sequence [J].

Chinkov, N ;

Majumdar, S ;

Marek, I .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (35) :10282-10283

[9] TANDEM CYCLOPROPANATION COPE REARRANGEMENT - A GENERAL-METHOD FOR THE CONSTRUCTION OF 7-MEMBERED RINGS [J].

DAVIES, HML .

TETRAHEDRON, 1993, 49 (24) :5203-5223

[10] Asymmetric synthesis of the tremulane skeleton by a tandem cyclopropanation/Cope rearrangement [J].

Davies, HML ;

Doan, BD .

TETRAHEDRON LETTERS, 1996, 37 (23) :3967-3970

← 1 2 3 4 5 6 7 →