Platinum(II)-Catalyzed Allylation of CO and CN Bonds under Hydrogenation Conditions

• Published in: Advanced synthesis & catalysis Vol. 352; no. 17; pp. 2949 - 2954
• Main Authors: Hong, Jong-Tai, Wang, Xi, Kim, Ji-Hwan, Kim, Kyunghee, Yun, Hoseop, Jang, Hye-Young
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 22.11.2010; WILEY‐VCH Verlag; Wiley
• Subjects: allylation; Chemistry; Chemistry, Applied; Chemistry, Organic; cyclization; hydrazones; hydrogenation; Physical Sciences; platinum; Science & Technology; METAL REAGENTS; REVERSE PRENYLATION; HOMOALLYLIC ALCOHOLS; ALDEHYDE OXIDATION LEVEL; ARYLATIVE CYCLIZATION; cyclization; hydrogenation; REDUCTIVE ALDOL; CATALYZED CARBONYL ALLYLATION; platinum; ALLENYL-ALDEHYDES; ARYL IODIDES; allylation; ALLYLIC TRANSFER-REACTION; hydrazones
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201000648

The nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and allene substrates were subject to hydrogenation conditions to generate nucleophilic allylplatinum complexes without using a stoichiometric amount of toxic and sensitive organometallic reagents. The allylplatinum intermediates reacted with CO and CN bonds to produce the corresponding homoallylic alcohol and amine derivatives in good yield. The Pt‐catalyzed allylation of CN bonds is the first example performed under hydrogenation conditions. A reaction mechanism initiated with the hydrometalation of allenes by PtH species is proposed based on deuterium labeling studies.