Ruthenium‐Catalyzed Dehydrogenation of Alcohols with Carbodiimide via a Hydrogen Transfer Mechanism

Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-Cu I -complexes and cyclic thiones when reacted with Cu I -salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)-center. This result demonstrates a convenient and facile access to CAAC-based Cu I -salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185 years Dumas' dream who tried to prepare the parent carbene (CH 2 ) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the OÀ H bond to the carbon(II)-center. This emphasizes the ability of carbon-compounds to mimic the reactivity of transition-metal complexes: reversible oxidative addition and reductive elimination of the OÀ H bond to/from the C(II)/C(IV)-centre.

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Realizing 1,1‐Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin‐2‐ols as a Source of Cyclic (Alkyl)(Amino)Carbenes

Das

¹

,

Elvers

²

,

Nayak

³

et al. 2022

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Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-Cu I -complexes and cyclic thiones when reacted with Cu I -salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)-center. This result demonstrates a convenient and facile access to CAAC-based Cu I -salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185 years Dumas' dream who tried to prepare the parent carbene (CH 2 ) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the OÀ H bond to the carbon(II)-center. This emphasizes the ability of carbon-compounds to mimic the reactivity of transition-metal complexes: reversible oxidative addition and reductive elimination of the OÀ H bond to/from the C(II)/C(IV)-centre.

show abstract

Ruthenium‐Catalyzed Dehydrogenation of Alcohols with Carbodiimide via a Hydrogen Transfer Mechanism

Abstract: Ruthenium-catalyzed oxidative dehydrogenation of alcohols using carbodiimide as an efficient hydrogen acceptor has been developed. The protocol exhibits wide substrate scope with good to excellent yields. The results of the kinetic

Cited by 5 publications

References 121 publications

Oxidation and Reduction

Oxidation and Reduction

Realizing 1,1‐Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin‐2‐ols as a Source of Cyclic (Alkyl)(Amino)Carbenes

Realizing 1,1‐Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin‐2‐ols as a Source of Cyclic (Alkyl)(Amino)Carbenes

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