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

Heiko Sommer; Tal Weissbrod; Ilan Marek

doi:10.1021/acscatal.9b00118

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

Heiko Sommer, Tal Weissbrod, Ilan Marek

Technion - Israel Institute of Technology

Research output: Contribution to journal › Article › peer-review

Abstract

An iridium-catalyzed tandem olefin migration/Cope rearrangement of alkenyl ω-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, ω-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.

Original language	English
Pages (from-to)	2400-2406
Number of pages	7
Journal	ACS Catalysis
Volume	9
Issue number	3
DOIs	https://doi.org/10.1021/acscatal.9b00118
State	Published - 1 Mar 2019

Keywords

Cope rearrangement
alkenyl cyclopropane
chain-walking remote functionalization
iridium catalysis

All Science Journal Classification (ASJC) codes

General Chemistry
Catalysis

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10.1021/acscatal.9b00118

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title = "A Tandem Iridium-Catalyzed {"}Chain-Walking{"}/Cope Rearrangement Sequence",

abstract = "An iridium-catalyzed tandem olefin migration/Cope rearrangement of alkenyl ω-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, ω-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.",

keywords = "Cope rearrangement, alkenyl cyclopropane, chain-walking remote functionalization, iridium catalysis",

author = "Heiko Sommer and Tal Weissbrod and Ilan Marek",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acscatal.9b00118",

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TY - JOUR

T1 - A Tandem Iridium-Catalyzed "Chain-Walking"/Cope Rearrangement Sequence

AU - Sommer, Heiko

AU - Weissbrod, Tal

AU - Marek, Ilan

PY - 2019/3/1

Y1 - 2019/3/1

N2 - An iridium-catalyzed tandem olefin migration/Cope rearrangement of alkenyl ω-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, ω-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.

AB - An iridium-catalyzed tandem olefin migration/Cope rearrangement of alkenyl ω-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, ω-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.

KW - Cope rearrangement

KW - alkenyl cyclopropane

KW - chain-walking remote functionalization

KW - iridium catalysis

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U2 - 10.1021/acscatal.9b00118

DO - 10.1021/acscatal.9b00118

M3 - مقالة

SN - 2155-5435

VL - 9

SP - 2400

EP - 2406

JO - ACS Catalysis

JF - ACS Catalysis

IS - 3

ER -

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

Abstract

Keywords

All Science Journal Classification (ASJC) codes

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