Palladium‐Catalyzed Carbo‐Oxygenation of Propargylic Amines using in Situ Tether Formation. Issue 12 (29th January 2019)

• Record Type: Journal Article
• Authors: Greenwood, Phillip D. G.; Grenet, Erwann; Waser, Jerome
• Is Part Of: Chemistry. Volume 25:Issue 12(2019)
• Page Start: 3010
• Page End: 3013
• Publication Date: 2019-01-29
• Subjects: alkynes -- amino alcohols -- palladium catalysis -- stereoselective synthesis -- tethers; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201900020
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 1, 2‐Amino alcohols and α‐aminocarbonyls are frequently found in natural products, drugs, chiral auxiliaries, and catalysts. This work reports a new method for the palladium‐catalyzed oxyalkynylation and oxyarylation of propargylic amines. The reaction is perfectly regioselective based on the in situ introduction of a hemiacetal tether derived from trifluoroacetaldehyde. cis ‐Selective carbo‐oxygenation was achieved for terminal alkynes, whereas internal alkynes gave trans ‐carbo‐oxygenation products. The obtained enol ethers could be easily transformed into 1, 2‐amino alcohols or α‐amino ketones using hydrogenation or hydrolysis, respectively. Abstract : Tether control : In situ tether formation allows the selective palladium‐catalyzed oxyalkynylation and oxyarylation of propargyl amines in high yield and selectivity. The obtained products are easily transformed into useful building blocks, such as amino ketones, amino alcohols, and furans.