Development and mechanistic studies of calcium-BINOL phosphate-catalyzed hydrocyanation of hydrazones.

ABSTRACT: Asymmetric hydrocyanation of hydrazones, catalyzed by a calcium-BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations. Trimethylsilyl cyanide (TMSCN) has been used as a sacrificial cyanide source. We found that isocyanide (rather than cyanide) is a preferred coordination to calcium during the catalytic cycle, while the active catalyst prefers a side-on coordination of cyanide. The configuration-determining step is a hydrocyanation via a calcium isocyanide complex, whereas the rate-limiting step is that which recovers the calcium catalyst and replaces the TMS-bound product from the catalys

SUBMITTER: Tortora C 

PROVIDER: S-EPMC12018919 | biostudies-literature | 2025

REPOSITORIES: biostudies-literature