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Regioselective Acetylation of Diols and Polyols by Acetate Catalysis: Mechanism and Application
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry. Cornell Univiversity, USA .
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2014 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 79, no 17, 8134-8142 p.Article in journal (Refereed) Published
Abstract [en]

We propose a principle for H-bonding activation in acylation of hydroxyl groups, where the acylation is activated by the formation of hydrogen bonds between hydroxyl groups and anions. With the guidance of this principle, we demonstrate a method for the selective acylation of carbohydrates. By this method, diols and polyols are regioselectively acetylated in high yields under mild conditions using catalytic amounts of acetate. In comparison to other methods involving reagents such as organotin, organoboron, organosilicon, organobase, and metal salts, this method is more environmentally friendly, convenient, and efficient and is also associated with higher regioselectivity. We have performed a thorough quantum chemical study to decipher the mechanism, which suggests that acetate first forms a dual H-bond complex with a diol, which enables subsequent monoacylation by acetic anhydride under mild conditions. The regioselectivity appears to originate from the inherent structure of the diols and polyols and their specific interactions with the coordinating acetate catalyst.

Place, publisher, year, edition, pages
2014. Vol. 79, no 17, 8134-8142 p.
National Category
Organic Chemistry
URN: urn:nbn:se:kth:diva-153258DOI: 10.1021/jo501343xISI: 000341345400036ScopusID: 2-s2.0-84923555817OAI: diva2:753991

QC 20141009

Available from: 2014-10-09 Created: 2014-10-03 Last updated: 2014-10-09Bibliographically approved

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Rahm, Martin
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