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The past decade has witnessed a rapid progress in asymmetric C−H activation. However, the enantioselective C−H alkoxylation and amination with alcohols and free amines remains elusive. Herein, we disclose the first enantioselective dehydrogenative C−H alkoxylation and amination enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The use of cheap and readily available cobalt(II) salts as catalysts and Saloxs as chiral ligands provides an efficient method to access P‐stereogenic compounds in excellent enantioselectivities (up to >99 % ee). The practicality of this protocol is demonstrated by gram‐scale preparation and further derivatizations of the resulting P‐stereogenic phosphinamides, which offering a flexible asymmetric alternative to access P‐stereogenic mono‐ and diphosphine chiral ligands. Preliminary mechanistic studies on the enantioselective C−H alkoxylation reaction suggest that a cobalt(III/IV/II) catalytic cycle might be involved. [ABSTRACT FROM AUTHOR]

The past decade has witnessed a rapid progress in asymmetric C−H activation. However, the enantioselective C−H alkoxylation and amination with alcohols and free amines remains elusive. Herein, we disclose the first enantioselective dehydrogenative C−H alkoxylation and amination enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The use of cheap and readily available cobalt(II) salts as catalysts and Saloxs as chiral ligands provides an efficient method to access P‐stereogenic compounds in excellent enantioselectivities (up to >99 % ee). The practicality of this protocol is demonstrated by gram‐scale preparation and further derivatizations of the resulting P‐stereogenic phosphinamides, which offering a flexible asymmetric alternative to access P‐stereogenic mono‐ and diphosphine chiral ligands. Preliminary mechanistic studies on the enantioselective C−H alkoxylation reaction suggest that a cobalt(III/IV/II) catalytic cycle might be involved. [ABSTRACT FROM AUTHOR]

Previous methods on CoIII‐catalyzed asymmetric C−H activation rely on the use of tailor‐made cyclopentadienyl‐ligated CoIII complexes, which require lengthy steps for the preparation. Herein, we report an unprecedented enantioselective C−H functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and chiral amino alcohols. A broad range of P‐stereogenic compounds were synthesized in high yields with excellent enantioselectivities (45 examples, up to 99 % yield and >99 % ee). The isolation and characterization of several intermediates provided insights into the generation of active catalytic cobalt species, the action of Salox, and the mode of stereocontrol. [ABSTRACT FROM AUTHOR]

Previous methods on CoIII‐catalyzed asymmetric C−H activation rely on the use of tailor‐made cyclopentadienyl‐ligated CoIII complexes, which require lengthy steps for the preparation. Herein, we report an unprecedented enantioselective C−H functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and chiral amino alcohols. A broad range of P‐stereogenic compounds were synthesized in high yields with excellent enantioselectivities (45 examples, up to 99 % yield and >99 % ee). The isolation and characterization of several intermediates provided insights into the generation of active catalytic cobalt species, the action of Salox, and the mode of stereocontrol. [ABSTRACT FROM AUTHOR]

Previous methods on CoIII‐catalyzed asymmetric C−H activation rely on the use of tailor‐made cyclopentadienyl‐ligated CoIII complexes, which require lengthy steps for the preparation. Herein, we report an unprecedented enantioselective C−H functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and chiral amino alcohols. A broad range of P‐stereogenic compounds were synthesized in high yields with excellent enantioselectivities (45 examples, up to 99 % yield and >99 % ee). The isolation and characterization of several intermediates provided insights into the generation of active catalytic cobalt species, the action of Salox, and the mode of stereocontrol. [ABSTRACT FROM AUTHOR]