10.1021/acsomega.7b01846.s002
Champak Dutta
Champak
Dutta
Debasish Ghorai
Debasish
Ghorai
Joyanta Choudhury
Joyanta
Choudhury
To “Rollover” or Not? Stereoelectronically
Guided C–H Functionalization Pathways from Rhodium–Abnormal
NHC Intermediates
American Chemical Society
2018
pyridine-imidazolium substrates
chelating molecules
work addresses
Catalytic reactions
rollover
transition-metal complexes
NHC
nonrollover
pathway
activation
N-heterocyclic carbene
stereoelectronic demand
Rollover
2018-02-07 19:22:00
Dataset
https://acs.figshare.com/articles/dataset/To_Rollover_or_Not_Stereoelectronically_Guided_C_H_Functionalization_Pathways_from_Rhodium_Abnormal_NHC_Intermediates/5866764
Rollover
C–H activation with transition-metal complexes
has been found to be a difficult but viable pathway to functionalize
potentially chelating molecules, which are otherwise reluctant to
react further. However, selective rollover or nonrollover C–H
activation pathway depends on the stereoelectronic demand of the associated
organometallic intermediate(s). The presented work addresses the above
issue on abnormal N-heterocyclic carbene (NHC) platform. Catalytic
reactions of pyridine-imidazolium substrates with internal alkynes
have been selectively guided toward either rollover or nonrollover
C–H functionalization route via fulfilling the steric and electronic
demands of the relevant rhodium(III)–abnormal NHC metallacyclic
intermediates.