期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 38, 页码 16572-16578出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202004354
关键词
acyl transfer; enantioselectivity; kinetic resolution; organocatalysis; tertiary alcohols
资金
- ERC under the European Union's Seventh Framework Programme (FP7/2007-2013)/E.R.C. grant [279850]
- Chinese Scholarship Scheme
- University of St Andrews
- Universidad Autnoma de Madrid
- EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) [EP/L016419/1]
- Royal Society for a Wolfson Research Merit Award
A highly enantioselective isothiourea-catalyzed acylative kinetic resolution (KR) of acyclic tertiary alcohols has been developed. Selectivity factors of up to 200 were achieved for the KR of tertiary alcohols bearing an adjacent ester substituent, with both reaction conversion and enantioselectivity found to be sensitive to the steric and electronic environment at the stereogenic tertiary carbinol centre. For more sterically congested alcohols, the use of a recently-developed isoselenourea catalyst was optimal, with equivalent enantioselectivity but higher conversion achieved in comparison to the isothiourea HyperBTM. Diastereomeric acylation transition state models are proposed to rationalize the origins of enantiodiscrimination in this process. This KR procedure was also translated to a continuous-flow process using a polymer-supported variant of the catalyst.
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