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A Boron Activating Effect Enables Cobalt-Catalyzed Asymmetric Hydrogenation of Sterically Hindered Alkenes
Peter Viereck1, Simon Krautwald1, Tyler P Pabst1
1Department of Chemistry , Princeton University , Princeton , New Jersey 08544 , United States.
Abstract:
Unsymmetric 1,1-diboryl alkenes bearing one -[BPin] (BPin = pinacolatoboryl) and one -[BDan] (BDan = 1,8-diaminonaphthalatoboryl) substituent each were hydrogenated in high yield and enantioselectivity using C1-symmetric pyridine(diimine) (PDI) cobalt complexes. High activities and stereoselectivities were observed with an array of 2-alkyl-, 2-aryl-, and 2-boryl-substituted 1,1-diboryl alkenes, giving rise to enantioenriched diborylalkane building blocks. Systematic study of substrate substituent effects identified competing steric and electronic demands in the key activating role of the boron substituents, whereby sterically unencumbered boronates such as -[BDan], -[BCat] (BCat = catecholatoboryl), and -[Beg] (Beg = ethylene glycolatoboryl) promote the hydrogenation of trisubstituted alkenes by enabling irreversible α-boron-directed insertion pathways to achieve otherwise challenging hydrogenations of trisubstituted alkenes. Deuterium-labeling studies with 1,1-diboryl alkenes support an insertion pathway generating a chiral intermediate with two different boron substituents and cobalt bound to the same carbon.
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