Chiral Counteranion Strategy for Asymmetric Oxidative C(sp3)H/C(sp3)H Coupling: Enantioselective α-Allylation of Aldehydes with Terminal Alkenes

• Published in: Angewandte Chemie International Edition Vol. 53; no. 45; pp. 12218 - 12221
• Main Authors: Wang, Pu-Sheng, Lin, Hua-Chen, Zhai, Yu-Jia, Han, Zhi-Yong, Gong, Liu-Zhu
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.11.2014; WILEY‐VCH Verlag; Wiley
• Subjects: allylic compounds; Chemistry; Chemistry, Multidisciplinary; cross-coupling; CH activation; enantioselectivity; palladium; Physical Sciences; Science & Technology; enantioselectivity; SP C-H; ACTIVATION; TERTIARY-AMINES; ALLYLIC ALKYLATION; BOND-CLEAVAGE; ADJACENT; HOMOALLYLIC DIAMINATION; CATALYSIS CONCEPT; C-H activation; PHOSPHORIC-ACID; allylic compounds; cross-coupling; palladium; METAL CATALYSIS; CH activation
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201408199

The first enantioselective α‐allylation of aldehydes with terminal alkenes has been realized by combining asymmetric counteranion catalysis and palladium‐catalyzed allylic CH activation. This method can tolerate a wide scope of α‐branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity. Importantly, the findings suggest a new strategy for the future creation of enantioselective CH/CH coupling reactions. Go with the combo: The title reaction is realized by combining asymmetric counteranion catalysis and palladium‐catalyzed allylic CH activation. This method tolerates a wide scope of α‐branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity.