期刊
CHEM
卷 7, 期 1, 页码 237-254出版社
CELL PRESS
DOI: 10.1016/j.chempr.2020.11.017
关键词
-
资金
- NIH [5R01GM121441]
- Amgen
- Princeton University
- Alfried Krupp von Bohlen und Halbach Foundation
This study reported synthetic and mechanistic investigations into the C(sp(2))-H borylation of various electronically diverse arenes catalyzed by bis(phosphine)pyridine ( IPr PNP) cobalt complexes. The research found that kinetic control of B-H and C(sp(2)-H) oxidative addition can result in para-to-ester and para-to-boronate ester selectivity, overriding previous ortho-to-fluorine regioselectivity. This demonstrates that subtle changes in the relative rates of individual steps of the catalytic cycle can enable unique and switchable site selectivities.
Synthetic and mechanistic investigations into the C(sp(2))-H borylation of various electronically diverse arenes catalyzed by bis(phosphine)pyridine ( IPr PNP) cobalt complexes are reported. Borylation of various benzoate esters and arylboronate esters gave remarkably high selectivities for the position para to the functional group; in both cases, this regioselectivity was found to override the orthoto-fluorine regioselectivity, previously reported for ((PNP)-P-iPr)Co borylation catalysts, which arises from thermodynamic control of C(sp(2))-H oxidative addition. Mechanistic studies support pathways that result in para-to-ester and para-to-boronate ester selectivity by kinetic control of B-H and C(sp(2)-H) oxidative addition, respectively. Borylation of a particularly electron-deficient fluorinated arylboronate ester resulted in acceleration of C(sp(2))-H oxidative addition and concomitant inversion of regioselectivity, demonstrating that subtle changes in the relative rates of individual steps of the catalytic cycle can enable unique and switchable site selectivities.
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