Recent Progress in the Use of Cyanophosphates as Synthetic Intermediates

Dedication

This review is dedicated to the 90th birthday of Professor Emeritus Takayuki Shioiri at Nagoya City University.

Abstract

The reaction of carbonyl compounds with diethyl phosphorocyanidate in the presence of a catalytic amount of lithium cyanide readily affords cyanophosphates (CPs), which have been utilized as useful intermediates for the introduction of a C₁ unit in a variety of reactions. This short review summarizes the progress made in the application of CPs and the related compounds in organic synthesis over the last decade, in which the following items are covered. 1) Introduction. 2) Synthesis of Succinonitrile by Homocoupling from CPs with Cp₂TiI. 3) Dearomative Allylation of Naphthaldehyde CPs by Palladium Catalysis. 4) Efficient Synthesis of a 5α-Reductase Inhibitor, 3-(Tetrazol-5-yl)-3,5-pregnadien-20-one through Allylic Rearrangement of CPs. 5) Generation of Alkylidene Carbenes through Tetrazole Fragmentation Derived from CPs. 6) Transformation of Benzaldehydes to Benzonitriles via CPs without One-Carbon Homologation. 7) Preparation of O-Phosphinoyl-protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles. 8) Miscellaneous Reactions. 9) Summary and Perspective.

Keywords

Diethyl phosphorocyanidate - Cyanophosphates - Homocoupling - Dearomative allylation - 5α-Reductase inhibitor - Alkylidene carbenes - Benzonitriles

Publication History

Received: 24 July 2025

Accepted after revision: 17 September 2025

Accepted Manuscript online:
17 September 2025

Article published online:
27 October 2025

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