Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 8, Pages 3984-3988Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202012768
Keywords
alkynes; carbon dioxide fixation; copper catalysis; hydroxymethylation; synthetic methods
Categories
Funding
- National Natural Science Foundation of China [21808164]
- Tianjin Key Science and Technology Project [19ZXNCGX00030]
- China Postdoctoral Science Foundation [2018M631744, 2020T130466]
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An intriguing strategy for copper-catalyzed hydroxymethylation of alkynes with CO2 and hydrosilane was developed. This strategy allows for selective triggering of direct hydroxymethylation and reductive hydroxymethylation, yielding a series of allylic alcohols and homobenzylic alcohols with high levels of Z/E, regio- and enantioselectivity. Such selectivity is attributed to the differences in response of vinylcopper intermediate to proton and CO2.
An intriguing strategy for copper-catalyzed hydroxymethylation of alkynes with CO2 and hydrosilane was developed. Switched on/off a proton source, for example, (BuOH)-Bu-t, direct hydroxymethylation and reductive hydroxymethylation could be triggered selectively, delivering a series of allylic alcohols and homobenzylic alcohols, respectively, with high levels of Z/E, regio- and enantioselectivity. Such a selective synthesis is attributed to the differences in response of vinylcopper intermediate to proton and CO2. The protonation of vinylcopper species is demonstrated to be prior to hydroxymethylation, thus allowing a diversion from direct alkyne hydroxymethylation to reductive hydroxymethylation in the presence of suitable proton.
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