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27.5.1.7 Method 7: Reaction of Carbanions and Thioformate Esters

DOI: 10.1055/sos-SD-027-00185

Collier, S. J.Science of Synthesis, (200427205.

Several stable thioaldehydes have been prepared through the treatment of carbanions with mono- and dithioformates.[‌14‌,‌15‌,‌122‌‌124‌] Thermodynamically stabilized monomeric thioaldehydes can be prepared through the treatment of β-iminonitriles 75 with potassium dithioformate in the presence of sodium 2-methylbutan-2-olate (Scheme 27). Yields vary widely, depending upon the imine substituent. Aprotic ethereal solvents such as tetrahydrofuran favor the reaction, whereas dipolar aprotic solvents are unsuitable. The resulting thioaldehydes 76 are remarkably stable and have well-defined melting points. NMR studies indicate that, in some cases, the thioaldehyde 76 is accompanied by small amounts of the corresponding tautomeric enethiol 77 or enamine 78.[‌122‌]

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