BROWSE

Related Scientist

Researcher

분자활성 촉매반응 연구단
분자활성 촉매반응 연구단
more info

Harnessing Secondary Coordination Sphere Interactions That Enable the Selective Amidation of Benzylic C-H Bonds

Cited 0 time in webofscience Cited 0 time in scopus
15 Viewed 2 Downloaded
Title
Harnessing Secondary Coordination Sphere Interactions That Enable the Selective Amidation of Benzylic C-H Bonds
Author(s)
Hoimin Jung; Malte Schrader; Dongwook Kim; Mu-Hyun Baik; Yoonsu Park; Sukbok Chang
Publication Date
2019-09
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.141, no.38, pp.15356 - 15366
Publisher
AMER CHEMICAL SOC
Abstract
Engineering site-selectivity is highly desirable especially in C-H functionalization reactions. We report a new catalyst platform that is highly selective for the amidation of benzylic C-H bonds controlled by pi-pi interactions in the secondary coordination sphere. Mechanistic understanding of the previously developed iridium catalysts that showed poor regioselectivity gave rise to the recognition that the pi-cloud of an aromatic fragment on the substrate can act as a formal directing group through an attractive noncovalent interaction with the bidentate ligand of the catalyst. On the basis of this mechanism-driven strategy, we developed a cationic (eta(5)-C5H5)Ru(II) catalyst with a neutral polypyridyl ligand to obtain record-setting benzylic selectivity in an intramolecular C-H lactamization in the presence of tertiary C-H bonds at the same distance. Experimental and computational techniques were integrated to identify the origin of this unprecedented benzylic selectivity, and robust linear free energy relationship between solvent polarity index and the measured site-selectivity was found to clearly corroborate that the solvophobic effect drives the selectivity. Generality of the reaction scope and applicability toward versatile gamma-lactam synthesis were demonstrated. © 2019 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/6440
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
Harnessing Secondary Coordination.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