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 journalArticle

7 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 languageEnglish
Pages (from-to)15373-15376
Number of pages4
JournalAngewandte Chemie - International Edition
Volume55
Issue number49
DOIs
Publication statusPublished - 2016 Jan 1
Externally publishedYes

Fingerprint

Rhodium
phosphine
Cycloaddition
Regioselectivity
Alkenes
Amides
Olefins
Electrons
Substrates

Keywords

  • asymmetric catalysis
  • cycloadditions
  • enamides
  • reaction mechanisms
  • rhodium

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition. / Masutomi, Koji; Sugiyama, Haruki; Uekusa, Hidehiro; Shibata, Yu; Tanaka, Ken.

In: Angewandte Chemie - International Edition, Vol. 55, No. 49, 01.01.2016, p. 15373-15376.

Research output: Contribution to journalArticle

Masutomi, Koji ; Sugiyama, Haruki ; Uekusa, Hidehiro ; Shibata, Yu ; Tanaka, Ken. / Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium-Catalyzed [2+2+2] Cycloaddition. In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 49. pp. 15373-15376.
@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",
year = "2016",
month = "1",
day = "1",
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 - 2016/1/1

Y1 - 2016/1/1

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

VL - 55

SP - 15373

EP - 15376

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 49

ER -