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- Title
Umpolung‐Enabled Divergent Dearomative Carbonylations.
- Authors
Wang, Ming‐Yang; Zeng, Wei‐Long; Chen, Lin; Yuan, Yu‐Fei; Li, Wei
- Abstract
Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three‐dimensional architectures, the case for simple arenes remains largely underdeveloped owing to the high aromatic stabilization energy. We herein report a dearomative sequential addition of two nucleophiles to arene π‐bonds through umpolung of chromium–arene complexes. This mode enables divergent dearomative carbonylation reactions of benzene derivatives by tolerating various nucleophiles in combination with alcohols or amines under CO‐gas‐free conditions, thus providing modular access to functionalized esters or amides. The tunable synthesis of 1,3‐ or 1,4‐cyclohexadienes as well as the construction of carbon quaternary centers further highlight the versatility of this dearomatization. Diverse late‐stage modifications and derivatizations towards synthetically challenging and bioactive molecules reveal the synthetic utility. A possible mechanism was proposed based on control experiments and intermediate tracking.
- Subjects
CARBONYLATION; NUCLEOPHILES; UMPOLUNG; AMIDES; DERIVATIZATION; BENZENE derivatives
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 33, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202403917