Mechanisms of bronsted acid catalyzed additions of phenols and protected amines to olefins: A DFT study

作者：Li Xin; Ye Siyu; He Chuan; Yu Zhi Xiang^*

来源：European Journal of Organic Chemistry, 2008, (25): 4296-4303.

DOI：10.1002/ejoc.200800337

• nucleophilic addition
• bronsted acids
• density functional calculations
• reaction mechanisms
• alkenes

DFT calculations at the B3LYP/6-31G(d) level were performed to understand the mechanism of the recently developed trifluoromethanesulfonic acid (TfOH) catalyzed intermolecular additions of phenols and protected amines to simple olefins. A novel mechanism involving a concerted, eight- membered-ring transition structure for the addition of the alcohol/amine to the alkene with TfOH as a catalyst was located. In the addition transition structure, the alkene sub-strafe is protonated and has significant carbocation character. Calculations to rationalize the relative reactivities of the alcohols and amines, together with the regioselectivity of amide addition to the diene, were also conducted. Factors affecting isomerization of the alkene substrates in the alcohol addition process are discussed.

• 出版日期2008-9
• 单位北京大学