Realizing 1,1-Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin-2-ols as a Source of Cyclic (Alkyl)(Amino)Carbenes.
Angew Chem Int Ed Engl
; 61(28): e202202637, 2022 Jul 11.
Article
in English
| MEDLINE | ID: covidwho-1919226
ABSTRACT
Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-CuI -complexes and cyclic thiones when reacted with CuI -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 CuI -salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185â
years Dumas' dream who tried to prepare the parent carbene (CH2 ) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the O-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 O-H bond to/from the C(II)/C(IV)-centre.
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MEDLINE
Language:
English
Journal:
Angew Chem Int Ed Engl
Year:
2022
Document Type:
Article
Affiliation country:
Anie.202202637
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