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While steric repulsion has been regarded as the key director of the observed high enantioselectivity for many years, we show that London dispersion (LD) interactions are at least as important for enantiodiscrimination. We exemplify this through a combination of detailed computational and experimental studies for a series of modified CBS catalysts equipped with dispersion energy donors (DEDs) in the catalysts and the substrates. Our results demonstrate that attractive LD interactions between the catalyst and the substrate, rather than steric repulsion, determine the selectivity. As a key outcome of our study, we were able to improve the catalyst design for some challenging CBS reductions.<\/jats:p>","DOI":"10.1002\/anie.202012760","type":"journal-article","created":{"date-parts":[[2020,11,18]],"date-time":"2020-11-18T18:47:56Z","timestamp":1605725276000},"page":"4823-4832","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":92,"title":["London Dispersion Interactions Rather than Steric Hindrance Determine the Enantioselectivity of the Corey\u2013Bakshi\u2013Shibata Reduction"],"prefix":"10.1002","volume":"60","author":[{"given":"Christian","family":"Eschmann","sequence":"first","affiliation":[{"name":"Institute of Organic Chemistry Justus Liebig University  35392 Giessen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lijuan","family":"Song","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry Justus Liebig University  35392 Giessen Germany"},{"name":"Current address: Shenzhen Bay Laboratory  Shenzhen 518055 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3608-5515","authenticated-orcid":false,"given":"Peter R.","family":"Schreiner","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry Justus Liebig University  35392 Giessen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,1,28]]},"reference":[{"key":"e_1_2_7_1_1","volume-title":"Intermolecular and surface forces","author":"Israelachvili J. 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