Nucleophile-Dependent Regioselective Reaction of (S)-4-Benzyl-2-Fluoroalkyl-1,3-Oxazolines

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• 作者：Haizhen Jiang ; Liuming Yan ; Minjun Xu ; Wenjun Lu ; Yeshan Cai ; Wen Wan ; Jianhua Yao ; Shaoxiong Wu ; Shizheng Zhu ; Jian Hao
• 刊名：The Journal of Organic Chemistry
• 出版年：2013
• 出版时间：May 3, 2013
• 年：2013
• 卷：78
• 期：9
• 页码：4261-4269
• 全文大小：463K
• 年卷期：v.78,no.9(May 3, 2013)
• ISSN：1520-6904

文摘

Nucleophile-dependent regioselectivities in the nucleophilic reaction of (S)-4-benzyl-2-fluoroalkyl-1,3-oxazoline to different types of fluorinated compounds were investigated experimentally and theoretically. The ring opening of (S)-4-benzyl-2-bromodifluoromethyl-1,3-oxazoline by arenethiolates exclusively occurred at the C5 position of the 1,3-oxazoline ring, whereas completely different regioselectivity was observed for a unimolecular radical nucleophilic substitution (S_RN1) at the terminal bromine atom of the CF₂Br group when arenolates were employed as the nucleophiles. The reaction of (S)-4-benzyl-2-trifluoromethyl-1,3-oxazoline with nucleophiles such as arenethiols, arenols, and TMSCl underwent nucleophilic ring opening in a regiospecific way, while the use of TMSCF₃ was determined to proceed through nucleophilic addition to the C鈺怤 bond.