Enantioselective Reductive Coupling of 1,3-Enynes to Heterocyclic Aromatic Aldehydes and Ketones via Rhodium-Catalyzed Asymmetric Hydrogenation:  Mechanistic Insight into the Role of Brønsted Acid Additives

• Published in: Journal of the American Chemical Society Vol. 128; no. 51; pp. 16448 - 16449
• Main Authors: Komanduri, Venukrishnan, Krische, Michael J
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 27.12.2006; Amer Chemical Soc
• Subjects: Acids - chemistry; Alcohols - chemical synthesis; Alcohols - chemistry; Aldehydes - chemistry; Alkynes - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Exact sciences and technology; General and physical chemistry; Hydrogenation; Ketones - chemistry; Kinetics and mechanisms; Molecular Structure; Organic chemistry; Oxidation-Reduction; Physical Sciences; Reactivity and mechanisms; Rhodium - chemistry; Science & Technology; Stereoisomerism; 1,6-ENYNES; ALKENYLZINC ADDITIONS; ALLYLIC ALCOHOLS; C BOND FORMATION; CONJUGATED ALKYNES; CARBONYL-COMPOUNDS; GENERATION; CYCLIZATION; HYDROFORMYLATION; PARTNERS; Catalytic reaction; Enantioselectivity; Transition metal; Aldehyde; Ketone; Hydrogenation; Enynic compound; Chemical reduction; Brönsted acid; Rhodium; Asymmetric synthesis; Reaction mechanism; Aromatic compound; Platinoid; Heterocyclic compound

Hydrogenation of 1,3-enynes 1a−e in the presence of heterocyclic aromatic aldehydes and ketones using chirally modified cationic rhodium precatalysts results in reductive coupling to afford dienylated α-hydroxy heteroarenes 2−23 with exceptional levels of regio- and enantiocontrol. Coupling of enyne...