α‐Alkyl‐α‐aryl (Trimethyltin) Nitriles: Versatile Nucleophilic Intermediates in Aldol‐Like Reactions

Abstract

α‐Alkyl‐α‐aryl (trimethyltin) nitriles react spontaneously with aldehydes and ketones in THF/toluene to give β‐hydroxy nitriles with satisfactory to good yields and diastereoselectivity. No extra catalyst is required in this aldol‐like reaction. A possible trimethyltin‐substituted ketene imine intermediate is invoked as reactive species. DFT calculations offer good support for this hypothesis.

DBU-Mediated Diastereoselective Aldol-Type Cyanomethylation of Isatins

“…Considering its wide application, significant work has been done toward the synthesis of functional cyanoalkyls. Specifically, stereochemical addition of nitrile enolates to aldehydes has been well investigated, although addition of nitrile enolates on ketones remains relatively less explored. In case where such additions have been attempted, the reaction has been low yielding due to its reversible nature.…”