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Dual Lewis Acid/Lewis Base Catalyzed Acylcyanation of Aldehydes: A Mechanistic Study
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-0596-0222
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2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 11, 3821-3829 p.Article in journal (Refereed) PublishedText
Abstract [en]

A mechanistic investigation, which included a Hammett correlation analysis, evaluation of the effect of variation of catalyst composition, and low-temperature NMR spectroscopy studies, of the Lewis acid-Lewis base catalyzed addition of acetyl cyanide to prochiral aldehydes provides support for a reaction route that involves Lewis base activation of the acyl cyanide with formation of a potent acylating agent and cyanide ion. The cyanide ion adds to the carbonyl group of the Lewis acid activated aldehyde. O-Acylation by the acylated Lewis base to form the final cyanohydrin ester occurs prior to decomplexation from titanium. For less reactive aldehydes, the addition of cyanide is the rate-determining step, whereas, for more reactive, electron-deficient aldehydes, cyanide addition is rapid and reversible and is followed by rate-limiting acylation. The resting state of the catalyst lies outside the catalytic cycle and is believed to be a monomeric titanium complex with two alcoholate ligands, which only slowly converts into the product.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2016. Vol. 22, no 11, 3821-3829 p.
Keyword [en]
asymmetric catalysis, Lewis acids, Lewis bases, reaction mechanisms, titanium
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-184528DOI: 10.1002/chem.201503782ISI: 000371741400037ScopusID: 2-s2.0-84959536218OAI: oai:DiVA.org:kth-184528DiVA: diva2:917432
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QC 20160406

Available from: 2016-04-06 Created: 2016-04-01 Last updated: 2016-04-06Bibliographically approved

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Laurell Nash, AnnaHertzberg, RobinDahlgren, BjörnBrinck, ToreMoberg, Christina
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