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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 37, Number 10
JKCSEZ 37(10)
August 20, 1993 

 
Title
Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines [Ⅲ] Palladium (0, Ⅱ)-Phosphine Complexes Catalyzed Cabonylation of Unsaturated Carboxylic Acids and It's Theoretical Studies

포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화 고리반응 (제 3 보). 팔라듐 (0, Ⅱ)-포스핀계 착물에 의한 불포화카르복실산의 카르보닐화 반응 및 그의 이론적 연구
Author
Myung-Ki Doh, Bong-Gon Kim, Maeng-Jun Jung, Young-Dae Song, Byung-Kak Park

도명기, 김봉곤, 정맹준, 송영대, 박병각
Keywords
Abstract
팔라듐(0, Ⅱ)-포스핀계 착물을 촉매로 하여 crotonic acid, methacrylic acid 및 3-butenoic acid 같은 불포화가크복실산의 카르보닐화 고리반응에서 생성가능한 물질의 구조를 확인하고, 그 반응메카니즘을 MM2 와 EHMO 계산에 의해서 추정하였다. 이 반응은 π-착물을 거쳐 금속 함유 고리화합물을 만든 다음 산화성 첨가반응과 환원성 제거반응이 일어나 진행된다. π-착물을 안정화시키는 crotonic acid, methacrylic acid 등은 카르보닐화 고리반응이 진행되지 않고, 3-butenoic acid는 무수카르복실산 유도체로서 glutaric anhydride와 3-methylsuccinic anhydride 및 이중결합이 자리옮김된 crotonic acid가 얻어졌다.

Reaction mechanism of palladium(0, Ⅱ)-phosphines complexes catalyzed cyclocarbonylation for unsaturated carboxylic acid such as crotonic acid, methacrylic acid and 3-butenoic acid has been investigated by product analysis, molecular mechanics and extended Huckel molecular orbital method. Reaction of 3-butenoic acid with palladium(0, Ⅱ)-phosphines catalyst gives palladium containing cycloester through intermediate palladium-olefin π-complex in the catalytic carbonylation. Palladium(0, Ⅱ)-phosphines complexes catalyze the cyclocarbonylation of 3-butenoic acid to give 3-methylsuccinic anhydride and glutaric anhydride. But π-complexes with palladium(0, Ⅱ)-phosphines and unsaturated carboxylic acids such as crotonic acid and methacrylic acid are not effective the catalytic cyclocarbonylation.

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903 - 909
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