DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes

Hideaki Takano, Natsuhiko Sugimura, Stephen Kyalo Kanyiva, Takanori Shibata

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition.

Original languageEnglish
Pages (from-to)5228-5234
Number of pages7
JournalACS Omega
Volume2
Issue number8
DOIs
Publication statusPublished - 2017 Jan 1

Fingerprint

Iridium
Cycloaddition
Alkenes
Discrete Fourier transforms
Olefins
Fluorenes
Density functional theory

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes. / Takano, Hideaki; Sugimura, Natsuhiko; Kanyiva, Stephen Kyalo; Shibata, Takanori.

In: ACS Omega, Vol. 2, No. 8, 01.01.2017, p. 5228-5234.

Research output: Contribution to journalArticle

@article{9763f221f8ab48cfb3bed1dc90a9cb1a,
title = "DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes",
abstract = "Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition.",
author = "Hideaki Takano and Natsuhiko Sugimura and Kanyiva, {Stephen Kyalo} and Takanori Shibata",
year = "2017",
month = "1",
day = "1",
doi = "10.1021/acsomega.7b00403",
language = "English",
volume = "2",
pages = "5228--5234",
journal = "ACS Omega",
issn = "2470-1343",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - DFT Studies on the Mechanism of the Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylene with Alkenes

AU - Takano, Hideaki

AU - Sugimura, Natsuhiko

AU - Kanyiva, Stephen Kyalo

AU - Shibata, Takanori

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition.

AB - Recently, we reported an Ir-catalyzed formal [4 + 1] cycloaddition of biphenylenes with alkenes, which gave 9,9-disubstituted fluorenes in moderate to excellent yields. We proposed a reaction mechanism that involved the intermolecular insertion of alkenes, β-elimination, and intramolecular insertion based on the results of experimental mechanistic studies. Herein, we further support the proposed mechanism by density functional theory calculations and explain why [4 + 1] cycloaddition proceeds rather than conventional [4 + 2] cycloaddition.

UR - http://www.scopus.com/inward/record.url?scp=85054502748&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85054502748&partnerID=8YFLogxK

U2 - 10.1021/acsomega.7b00403

DO - 10.1021/acsomega.7b00403

M3 - Article

VL - 2

SP - 5228

EP - 5234

JO - ACS Omega

JF - ACS Omega

SN - 2470-1343

IS - 8

ER -