Theoretical study of cyano-promoted intramolecular aza-Diels–Alder reaction

Chin Hung Lai; Cheng En Yang; Yang Chang Wu; Youness El Bakri; Eduardo Chamorro; Ta Hsien Chuang

doi:10.1002/poc.4466

Theoretical study of cyano-promoted intramolecular aza-Diels–Alder reaction

Chin Hung Lai, Cheng En Yang, Yang Chang Wu, Youness El Bakri, Eduardo Chamorro, Ta Hsien Chuang

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

Abstract

In this study, we attempted to explain why the substitution of a cyano group onto the 1-azadiene moiety promotes N-(2,3-diphenylallylidene)pent-4-en-1-amine to undergo an intramolecular aza-Diels–Alder reaction. Our M06-2X study found that the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine has an inverse electron demand. Therefore, the attachment of a cyano group to the diene moiety (1-azadiene) makes the intramolecular aza-Diels–Alder reaction feasible. Moreover, the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine was found to be a kinetically controlled reaction.

Original language	English
Journal	Journal of Physical Organic Chemistry
DOIs	https://doi.org/10.1002/poc.4466
Publication status	Accepted/In press - 2022

Keywords

aza-Diels–Alder reaction
density functional theory
local reactivity descriptors
natural bond analysis

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

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10.1002/poc.4466

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@article{b4e42328acc54e13b49a05ff05418c34,

title = "Theoretical study of cyano-promoted intramolecular aza-Diels–Alder reaction",

abstract = "In this study, we attempted to explain why the substitution of a cyano group onto the 1-azadiene moiety promotes N-(2,3-diphenylallylidene)pent-4-en-1-amine to undergo an intramolecular aza-Diels–Alder reaction. Our M06-2X study found that the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine has an inverse electron demand. Therefore, the attachment of a cyano group to the diene moiety (1-azadiene) makes the intramolecular aza-Diels–Alder reaction feasible. Moreover, the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine was found to be a kinetically controlled reaction.",

keywords = "aza-Diels–Alder reaction, density functional theory, local reactivity descriptors, natural bond analysis",

author = "Lai, {Chin Hung} and Yang, {Cheng En} and Wu, {Yang Chang} and {El Bakri}, Youness and Eduardo Chamorro and Chuang, {Ta Hsien}",

note = "Publisher Copyright: {\textcopyright} 2022 John Wiley & Sons Ltd.",

year = "2022",

doi = "10.1002/poc.4466",

language = "English",

journal = "Journal of Physical Organic Chemistry",

issn = "0894-3230",

publisher = "John Wiley and Sons Ltd",

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TY - JOUR

T1 - Theoretical study of cyano-promoted intramolecular aza-Diels–Alder reaction

AU - Lai, Chin Hung

AU - Yang, Cheng En

AU - Wu, Yang Chang

AU - El Bakri, Youness

AU - Chamorro, Eduardo

AU - Chuang, Ta Hsien

PY - 2022

Y1 - 2022

N2 - In this study, we attempted to explain why the substitution of a cyano group onto the 1-azadiene moiety promotes N-(2,3-diphenylallylidene)pent-4-en-1-amine to undergo an intramolecular aza-Diels–Alder reaction. Our M06-2X study found that the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine has an inverse electron demand. Therefore, the attachment of a cyano group to the diene moiety (1-azadiene) makes the intramolecular aza-Diels–Alder reaction feasible. Moreover, the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine was found to be a kinetically controlled reaction.

AB - In this study, we attempted to explain why the substitution of a cyano group onto the 1-azadiene moiety promotes N-(2,3-diphenylallylidene)pent-4-en-1-amine to undergo an intramolecular aza-Diels–Alder reaction. Our M06-2X study found that the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine has an inverse electron demand. Therefore, the attachment of a cyano group to the diene moiety (1-azadiene) makes the intramolecular aza-Diels–Alder reaction feasible. Moreover, the intramolecular aza-Diels–Alder reaction of N-(2,3-diphenylallylidene)pent-4-en-1-amine was found to be a kinetically controlled reaction.

KW - aza-Diels–Alder reaction

KW - density functional theory

KW - local reactivity descriptors

KW - natural bond analysis

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U2 - 10.1002/poc.4466

DO - 10.1002/poc.4466

M3 - Article

AN - SCOPUS:85142881284

SN - 0894-3230

JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

ER -

Theoretical study of cyano-promoted intramolecular aza-Diels–Alder reaction

Abstract

Keywords

ASJC Scopus subject areas

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