Realizing 1,1-Dehydration of secondary alcohols to carbenes: pyrrolidin-2-ols as a source of cyclic (Alkyl)(Amino)carbenes
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Dosyalar
Tarih
2022
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Wiley-VCH Verlag
Erişim Hakkı
info:eu-repo/semantics/embargoedAccess
Özet
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 (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.
Açıklama
Anahtar Kelimeler
1-Dehydration, Carbenes, Dehydrogenation, Elimination, Hydrated Carbenes
Kaynak
Angewandte Chemie International Edition
WoS Q Değeri
Q1
Scopus Q Değeri
Q1
Cilt
-
Sayı
-
