Abstract
A titanium‐catalyzed mono‐decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst‐controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two TiIII species in the C−C cleavage is proposed, and the beneficial role of added ZnCl2 and 2,4,6‐collidine hydrochloride is investigated.
Highlights
A titanium-catalyzed mono-decyanation of geminal dinitriles is reported
Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations
With the goal to close this methodological gap, we report a broadly applicable catalytic reductive decyanation that proceeds in the presence of a titanium(III) single-electron-transfer catalyst.[11,12]
Summary
A titanium-catalyzed mono-decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations.
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