Aromatic Claisen Rearrangements of Benzyl Ketene Acetals: Conversion of Benzylic Alcohols to (ortho‐Tolyl)acetates. Issue 2 (12th December 2016)

• Record Type: Journal Article
• Authors: Burns, Jed M.; Krenske, Elizabeth H.; McGeary, Ross P.
• Is Part Of: European journal of organic chemistry. Issue 2(2017)
• Page Start: 252
• Page End: 256
• Publication Date: 2016-12-12
• Subjects: Sigmatropic rearrangement -- Benzyl alcohols -- Ketene acetals -- Density functional calculations -- Pericyclic reactions; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201601354
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Claisen rearrangements of benzyl vinyl ethers are much less facile than those of aliphatic allyl vinyl ethers, and their synthetic utility has remained relatively unexplored. A one‐pot procedure is reported for the generation and Claisen rearrangement of benzyl vinyl ethers that contain an activating α‐alkoxy substituent on the vinyl group. A [3, 3]‐sigmatropic mechanism was supported by trapping of the intermediate isotoluene in an intramolecular Alder–ene reaction. Abstract : A one‐pot procedure is reported for the generation and Claisen rearrangement of benzyl vinyl ethers that contain an activating α‐alkoxy substituent on the vinyl group. A [3, 3]‐sigmatropic mechanism was supported by trapping of the intermediate isotoluene in an intramolecular Alder–ene reaction.