Enantioselective Palladium‐Catalyzed Carbonylative Carbocyclization of Enallenes via Cross‐Dehydrogenative Coupling with Terminal Alkynes: Efficient Construction of α‐Chirality of Ketones. Issue 16 (27th March 2017)

• Record Type: Journal Article
• Authors: Yang, Bin; Qiu, Youai; Jiang, Tuo; Wulff, William D.; Yin, Xiaopeng; Zhu, Can; Bäckvall, Jan‐E.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 16(2017)
• Page Start: 4535
• Page End: 4539
• Publication Date: 2017-03-27
• Subjects: asymmetric carbocyclization -- enallenes -- homogeneous catalysis -- oxidation -- palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201612385
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: An enantioselective Pd II /Brønsted acid‐catalyzed carbonylative carbocyclization of enallenes ending with a cross‐dehydrogenative coupling (CDC) with a terminal alkyne was developed. VAPOL phosphoric acid was found as the best co‐catalyst among the examined 28 chiral acids, for inducing the enantioselectivity of α‐chiral ketones. As a result, a number of chiral cyclopentenones were easily synthesized in good to excellent enantiomeric ratio with good yields. Abstract : From CO to ketones with the introduction of α‐chirality : A Pd II /Brønsted acid‐catalyzed enantioselective carbonylation–carbocyclization of enallenes has been developed, proceeding through an efficient CO and olefin insertion cascade to yield ketones with α‐chirality. A number of chiral cyclopentenones could be easily synthesized in good to excellent enantioselectivity and good yields.