Catalytic Synthesis of Dibenzazepines and Dibenzazocines by 7-Exo- and 8-Endo-Dig-Selective Cycloisomerization

Mamoru Ito; Asahi Takaki; Moeka Okamura; Kyalo Stephen Kanyiva; Takanori Shibata

doi:10.1002/ejoc.202001643

Catalytic Synthesis of Dibenzazepines and Dibenzazocines by 7-Exo- and 8-Endo-Dig-Selective Cycloisomerization

Mamoru Ito^*, Asahi Takaki, Moeka Okamura, Kyalo Stephen Kanyiva, Takanori Shibata^*

^*Corresponding author for this work

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

10 Citations (Scopus)

Abstract

The 7-exo- and 8-endo-dig-selective gold-catalyzed cycloisomerizations of 2-propargylamino biphenyl derivatives were developed. The reaction of terminal alkynes gave dibenzo[b,d]azepines by 7-exo-dig cycloisomerization. In contrast, when internal alkynes were subjected to the reaction, 8-endo-dig cycloisomerization proceeded to provide dibenzo[b,d]azocines. The nucleophilicity at the reaction site and the electron-withdrawing effect of a tosyl group were important for the present selective transformation. This protocol could be used for ynamide substrates and a silver-catalyzed reaction gave 7-exo-dig products selectively.

Original language	English
Pages (from-to)	1688-1692
Number of pages	5
Journal	European Journal of Organic Chemistry
Volume	2021
Issue number	11
DOIs	https://doi.org/10.1002/ejoc.202001643
Publication status	Published - 2021 Mar 19

Keywords

7-Exo-dig
8-Endo-dig
Cycloisomerization
Gold catalysis
NHC ligands

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

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10.1002/ejoc.202001643

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@article{924c91ad604e494998e1c3b9c4c26660,

title = "Catalytic Synthesis of Dibenzazepines and Dibenzazocines by 7-Exo- and 8-Endo-Dig-Selective Cycloisomerization",

abstract = "The 7-exo- and 8-endo-dig-selective gold-catalyzed cycloisomerizations of 2-propargylamino biphenyl derivatives were developed. The reaction of terminal alkynes gave dibenzo[b,d]azepines by 7-exo-dig cycloisomerization. In contrast, when internal alkynes were subjected to the reaction, 8-endo-dig cycloisomerization proceeded to provide dibenzo[b,d]azocines. The nucleophilicity at the reaction site and the electron-withdrawing effect of a tosyl group were important for the present selective transformation. This protocol could be used for ynamide substrates and a silver-catalyzed reaction gave 7-exo-dig products selectively.",

keywords = "7-Exo-dig, 8-Endo-dig, Cycloisomerization, Gold catalysis, NHC ligands",

author = "Mamoru Ito and Asahi Takaki and Moeka Okamura and Kanyiva, {Kyalo Stephen} and Takanori Shibata",

note = "Funding Information: This work was supported by Waseda University Grant for Special Research Projects (2019C‐565). Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = mar,

day = "19",

doi = "10.1002/ejoc.202001643",

language = "English",

volume = "2021",

pages = "1688--1692",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley-VCH Verlag",

number = "11",

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TY - JOUR

T1 - Catalytic Synthesis of Dibenzazepines and Dibenzazocines by 7-Exo- and 8-Endo-Dig-Selective Cycloisomerization

AU - Ito, Mamoru

AU - Takaki, Asahi

AU - Okamura, Moeka

AU - Kanyiva, Kyalo Stephen

AU - Shibata, Takanori

PY - 2021/3/19

Y1 - 2021/3/19

N2 - The 7-exo- and 8-endo-dig-selective gold-catalyzed cycloisomerizations of 2-propargylamino biphenyl derivatives were developed. The reaction of terminal alkynes gave dibenzo[b,d]azepines by 7-exo-dig cycloisomerization. In contrast, when internal alkynes were subjected to the reaction, 8-endo-dig cycloisomerization proceeded to provide dibenzo[b,d]azocines. The nucleophilicity at the reaction site and the electron-withdrawing effect of a tosyl group were important for the present selective transformation. This protocol could be used for ynamide substrates and a silver-catalyzed reaction gave 7-exo-dig products selectively.

AB - The 7-exo- and 8-endo-dig-selective gold-catalyzed cycloisomerizations of 2-propargylamino biphenyl derivatives were developed. The reaction of terminal alkynes gave dibenzo[b,d]azepines by 7-exo-dig cycloisomerization. In contrast, when internal alkynes were subjected to the reaction, 8-endo-dig cycloisomerization proceeded to provide dibenzo[b,d]azocines. The nucleophilicity at the reaction site and the electron-withdrawing effect of a tosyl group were important for the present selective transformation. This protocol could be used for ynamide substrates and a silver-catalyzed reaction gave 7-exo-dig products selectively.

KW - 7-Exo-dig

KW - 8-Endo-dig

KW - Cycloisomerization

KW - Gold catalysis

KW - NHC ligands

UR - http://www.scopus.com/inward/record.url?scp=85102688448&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85102688448&partnerID=8YFLogxK

U2 - 10.1002/ejoc.202001643

DO - 10.1002/ejoc.202001643

M3 - Article

AN - SCOPUS:85102688448

SN - 1434-193X

VL - 2021

SP - 1688

EP - 1692

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 11

ER -

Catalytic Synthesis of Dibenzazepines and Dibenzazocines by 7-Exo- and 8-Endo-Dig-Selective Cycloisomerization

Abstract

Keywords

ASJC Scopus subject areas

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