Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition

Koji Masutomi; Haruki Sugiyama; Hidehiro Uekusa; Yu Shibata; Ken Tanaka

doi:10.1002/anie.201608952

Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition

Koji Masutomi, Haruki Sugiyama, Hidehiro Uekusa, Yu Shibata, Ken Tanaka

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

18 Citations (Scopus)

Abstract

It has been established that cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asymmetric [2+2+2] cycloaddition of 1,6-enynes with electron-rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Interestingly, regioselectivity depends on structures of substrates. The present cycloaddition was successfully applied to the enantioselective total synthesis of (−)-porosadienone by using the amide moiety as a leaving group.

Original language	English
Pages (from-to)	15373-15376
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	49
DOIs	https://doi.org/10.1002/anie.201608952
Publication status	Published - 2016 Dec 5
Externally published	Yes

Keywords

asymmetric catalysis
cycloadditions
enamides
reaction mechanisms
rhodium

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201608952

Cite this

@article{12a2903035004b53b3d5e96a1f826c15,

title = "Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition",

abstract = "It has been established that cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asymmetric [2+2+2] cycloaddition of 1,6-enynes with electron-rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Interestingly, regioselectivity depends on structures of substrates. The present cycloaddition was successfully applied to the enantioselective total synthesis of (−)-porosadienone by using the amide moiety as a leaving group.",

keywords = "asymmetric catalysis, cycloadditions, enamides, reaction mechanisms, rhodium",

author = "Koji Masutomi and Haruki Sugiyama and Hidehiro Uekusa and Yu Shibata and Ken Tanaka",

note = "Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = dec,

day = "5",

doi = "10.1002/anie.201608952",

language = "English",

volume = "55",

pages = "15373--15376",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "49",

}

TY - JOUR

T1 - Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition

AU - Masutomi, Koji

AU - Sugiyama, Haruki

AU - Uekusa, Hidehiro

AU - Shibata, Yu

AU - Tanaka, Ken

PY - 2016/12/5

Y1 - 2016/12/5

N2 - It has been established that cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asymmetric [2+2+2] cycloaddition of 1,6-enynes with electron-rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Interestingly, regioselectivity depends on structures of substrates. The present cycloaddition was successfully applied to the enantioselective total synthesis of (−)-porosadienone by using the amide moiety as a leaving group.

AB - It has been established that cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asymmetric [2+2+2] cycloaddition of 1,6-enynes with electron-rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Interestingly, regioselectivity depends on structures of substrates. The present cycloaddition was successfully applied to the enantioselective total synthesis of (−)-porosadienone by using the amide moiety as a leaving group.

KW - asymmetric catalysis

KW - cycloadditions

KW - enamides

KW - reaction mechanisms

KW - rhodium

UR - http://www.scopus.com/inward/record.url?scp=84997633405&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84997633405&partnerID=8YFLogxK

U2 - 10.1002/anie.201608952

DO - 10.1002/anie.201608952

M3 - Article

AN - SCOPUS:84997633405

SN - 1433-7851

VL - 55

SP - 15373

EP - 15376

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 49

ER -

Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this