Efficient One‐Pot Multifunctionalization of Alkynes en Route to α‐Alkoxyketones, α‐Thioketones, and α‐Thio Thioketals by using an Umpolung Strategy. Issue 57 (16th August 2017)

• Record Type: Journal Article
• Authors: Xu, Zhou; Zhai, Rongliang; Liang, Ting; Zhang, Liming
• Is Part Of: Chemistry. Volume 23:Issue 57(2017)
• Page Start: 14133
• Page End: 14137
• Publication Date: 2017-08-16
• Subjects: alkynes -- umpolung -- sulfur -- thioketals -- thioketones; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201703087
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The use of polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of unique substances. Herein, a new approach for α‐oxygenated ketones, α‐thioketones and α‐thio thioketals via an intermolecular umpolung reaction between nucleophiles (alcohols/thioalcohols) and N ‐alkenoxypyridinium salts, which were generated from the corresponding alkynes, has been developed for the first time. The reactions proceed with good substrate scope and excellent functional group tolerance in one‐pot manner. Applications of the products, α‐oxygenated ketones, to the synthesis of other valuable synthetic moieties has also been successfully achieved. Abstract : All topsy turvy : A new and broadly applicable method for the synthesis of unique α‐oxygenated ketones, α‐thio ketones and α‐thio thioketals via umpolung reaction of nucleophiles‐alcohols/thioalcohols and N ‐alkenoxypyridinium salts generated from alkynes in a one‐pot manner is reported for the first time. The reaction is controllable and tunable with good substrates scope (46 examples) and excellent functional group tolerance (see schemes).