Umpolung‐Enabled Divergent Dearomative Carbonylations

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three-dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π-bonds through umpolung chromium-arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO-gas-free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3- 1,4-cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late-stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

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Umpolung‐Enabled Divergent Dearomative Carbonylations

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Abstract Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three‐dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π‐bonds through umpolung chromium–arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO‐gas‐free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3‐ 1,4‐cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late‐stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

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Dearomative 1,2‐(Deutero)Hydrotrifluoromethylation of Chromium‐Bound Arenes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(20), P. 4199 - 4204

Published: July 19, 2024

Abstract Dearomative trifluoromethylation of arenes provides an ideal method for constructing CF 3 ‐containing three‐dimensional architectures which are increasing interest in drug discovery. However, such transformation is rare and challenging because the inherently low reactivity arene π‐systems selectivity issues. Herein, we disclose a general dearomative 1,2‐hydrotrifluoromethylation (hetero)arenes utilizing activation by temporary π‐complexation to chromium, thus affording convenient access 1,3‐cyclohexadienes bearing privileged group. The versatility this strategy further enables 1,2‐deuterotrifluoromethylation with high deuterated ratios. related 1,2‐(deutero)hydroperfluoroethylation reactions were conducted well range chromium‐bound (hetero)arenes. Finally, reasonable mechanism was proposed based on intermediate capture control experiments.

Language: Английский

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Chromium‐Mediated Dearomative Allylic Addition to Arenes

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(46)

Published: Aug. 23, 2024

Abstract In comparison with the well‐established allylic additions to C=O, C=N, and C=C double bonds, dearomative addition arene π‐systems is heavily underdeveloped due severe challenge in breaking aromatic resonance stabilization. Herein, we disclose a general efficient chromium‐bound arenes using allylsilanes as pronucleophiles, thus affording convenient access allyl‐functionalized 1,3‐cyclohexadiene building blocks. With commercially available deuterium sources, versatility of this strategy further enables an 1,2‐deuteroallylation high level incorporation. Finally, preliminary try on asymmetric hydroallylation based chiral auxiliary described.

Language: Английский

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