BROWSE

Related Scientist

Researcher

분자활성 촉매반응 연구단
분자활성 촉매반응 연구단
more info

Rationally Designing Regiodivergent Dipolar Cycloadditions: Frontier Orbitals Show How To Switch between [5+3] and [4+2] Cycloadditions

Cited 0 time in webofscience Cited 0 time in scopus
10 Viewed 0 Downloaded
Title
Rationally Designing Regiodivergent Dipolar Cycloadditions: Frontier Orbitals Show How To Switch between [5+3] and [4+2] Cycloadditions
Author(s)
Seung-yeol Baek; Ju Young Lee; Donguk Ko; Mu-Hyun Baik; Eun Jeong Yoo
Publication Date
2018-07
Journal
ACS CATALYSIS, v.8, no.7, pp.6353 - 6361
Publisher
AMER CHEMICAL SOC
Abstract
A pyridinium zwitterion substrate is employed with two different types of transition metal catalysts to develop a regiodivergent cycloaddition. The pyridinium zwitterion is a highly reactive dipolar substrate that can undergo a dipolar cycloaddition with various reactants. It has multiple reaction sites, and the chemoselectivity is determined by the electronic demand of the catalyst substrate complex. The reaction with nucleophilic Pd reagents affords fused N-heterocyclic compounds via regioselective [4 + 2] cycloaddition. The origin of the site selectivity and the mechanism of this reaction are investigated in this combined experimental and computational study. We found that the pyridinium zwitterion plays a completely different role in the palladium(0)-catalyzed [4 + 2] cycloaddition reaction and in the rhodium(II)-catalyzed [5 + 3] cycloaddition, which was examined experimentally in a previous study. The frontier molecular orbitals of the pyridinium substrate and activated catalyst complex reveal that the pyridinium zwitterion can act as both a nucleophile and an electrophile depending on the reaction partner in a manner much more defined than that of conventional substrates, leading to the observed regiodivergent chemical reactivity.
URI
https://pr.ibs.re.kr/handle/8788114/5923
ISSN
2155-5435
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
baik_Rationally Designing_acscatal.8b00845.pdfDownload

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse