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In the present study, the detailed reaction mechanism and, in particular, the origin of the observed high chemoselectivity, have been studied with DFT calculations. The catalytic cycle mainly consisted of three steps: 1,2\u2010addition, hydride transfer, and acyl transfer steps. The calculation results reproduce the experimental observations that 4\u2010chlorobenzaldehyde acts as the hydrogen donor (carbonyl part in the ester product), while 2\u2010methoxybenzaldehyde acts as the hydrogen acceptor (alcohol part in the product). The two main factors are responsible for such chemoselectivity: 1)\u2005in the rate\u2010determining hydride transfer step, the <jats:italic>para<\/jats:italic>\u2010chloride substituent facilitates the hydride\u2010donating process by weakening the steric hindrance, and 2)\u2005the <jats:italic>ortho<\/jats:italic>\u2010methoxy substituent facilitates the hydride\u2010accepting process by stabilizing the magnesium center (by compensating for the electron deficiency).<\/jats:p>","DOI":"10.1002\/asia.201402746","type":"journal-article","created":{"date-parts":[[2014,9,11]],"date-time":"2014-09-11T16:47:28Z","timestamp":1410454048000},"page":"3472-3481","source":"Crossref","is-referenced-by-count":6,"title":["Mechanistic Origin of Chemoselectivity in Thiolate\u2010Catalyzed Tishchenko Reactions"],"prefix":"10.1002","volume":"9","author":[{"given":"Hai\u2010Zhu","family":"Yu","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xue\u2010Jiao","family":"Tian","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xiang","family":"Lin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Guo\u2010Hua","family":"Hu","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhi\u2010Min","family":"Dang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,9,11]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","first-page":"355","volume":"38","author":"Tischtschenko W.","year":"1906","journal-title":"J. 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