Access to Enantiopure Triarylmethanes and 1, 1‐Diarylalkanes by NHC‐Catalyzed Acylative Desymmetrization. Issue 10 (25th January 2017)

• Record Type: Journal Article
• Authors: Lu, Shenci; Song, Xiaoxiao; Poh, Si Bei; Yang, Hui; Wong, Ming Wah; Zhao, Yu
• Is Part Of: Chemistry. Volume 23:Issue 10(2017)
• Page Start: 2275
• Page End: 2281
• Publication Date: 2017-01-25
• Subjects: 1, 1-diarylalkanes -- acylation -- carbenes -- desymmetrization -- N-heterocycles; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201605445
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: We present herein an unprecedented, efficient and enantioselective synthesis of triarylmethanes and 1, 1‐diarylalkanes through N‐heterocyclic carbene‐catalyzed acylative desymmetrization of bisphenols. This method utilizes readily available substrates, reagents and a simple procedure to deliver the valuable products in excellent enantiopurity. DFT calculations reveal that the selectivity is governed by the C−C bond cleavage step of the tetrahedral intermediate leading to the ester product. A transition state model featuring a combination of intramolecular hydrogen bond and steric effect is developed to explain the enantioselectivity. Abstract : Three′s the charm : We present herein a general, efficient and enantioselective synthesis of triarylmethanes and 1, 1‐diarylalkanes through N‐heterocyclic carbene‐catalyzed acylative desymmetrization of bisphenols. This method utilizes readily available substrates, reagents and a simple procedure to deliver the valuable products in excellent enantiopurity. DFT calculations provided a transition‐state model featuring a combination of intramolecular hydrogen bond and steric effect to explain the enantioselectivity.