Metal-Free Catalytic Reduction of α,β-Unsaturated Esters by 1,3,2-Diazaphospholene and Subsequent C–C Coupling with Nitriles

5 years ago

Metal-Free Catalytic Reduction of α,β-Unsaturated Esters by 1,3,2-Diazaphospholene and Subsequent C–C Coupling with Nitriles

Che Chang Chong, Rei Kinjo, Bin Rao

1,3,2-Diazaphospholene 1 catalyzes the conjugate transfer hydrogenation as well as the 1,4-hydroboration of α,β-unsaturated esters. The initial step for both processes involves a 1,4-hydrophosphination of the α,β-unsaturated esters to afford a phosphinyl enol ether. Subsequent cleavage of the P–O bond in the phosphinyl enol ether by ammonia-borane (AB) generates an enol intermediate which tautomerizes to saturated esters, while the P–O bond cleavage by HBpin via a formal σ-bond metathesis affords boryl enolate intermediate. The latter could undergo a further coupling reaction with nitriles to form substituted amino diesters or 1,3-imino esters, depending on α,β-unsaturated ester substrates. These catalytic reactions can also be performed in a one-pot manner, illustrating a protocol for metal-free catalytic C–C bond construction.

Publisher URL: http://dx.doi.org/10.1021/acscatal.7b01338

DOI: 10.1021/acscatal.7b01338