Olefin Insertion Reactivity of a (Phosphine-arenesulfonate)Palladium(II) Fluoride Complex
Olefin Insertion Reactivity of a (Phosphine-arenesulfonate)Palladium(II) Fluoride Complex
复制标题
DOI：
10.1021/acs.organomet.9b00545
复制
发表时间：
2019-10
期刊：
影响因子：
2.8
通讯作者：
R. Black;Stefan M. Kilyanek;Erik D. Reinhart;R. F. Jordan
中科院分区：
文献类型：
--
作者：
R. Black;Stefan M. Kilyanek;Erik D. Reinhart;R. F. Jordan
介绍了磷-芳烃磺酸Pd（II）氟配合物（PO-OMe）PdF(lut) (2, PO-OMe = P（2- ome - ph)2(2- so3 -5- me - ph), lut = 2,6-lutidine）的合成及其与缺电子烯烃的反应。（PO-OMe）PdBr(lut)(1)与AgF反应得到82:18的顺式p，F和反式p，F异构体混合物。在CD2Cl2溶液中，在室温下约3天内异构成1:2顺式p，F：反式p，F平衡混合物。2与氟化乙烯（VF）反应生成（PO-OMe）Pd(CH2CHF2)(lut)(3)，以顺式p，C异构体的形式存在。2与乙烯基溴（VBr）反应生成1和VF，通过初始氟化形成（PO-OMe）Pd(CH2CHBrF)(lut)（4，未观察到），然后消除β-Br。2与醋酸乙烯酯反应生成（PO-OMe）Pd{CH2CHF(OAc)}(lut)(5)，进一步反应形成c结合的烯酸酯络合物（PO-OMe）Pd{CH2C(= O)H}(lut)(6)和乙酰氟。2以类似的方式与苯甲酸乙烯酯反应。顺式- p，F-和反式- p，F…
The synthesis of the phosphine-arenesulfonate Pd(II) fluoride complex (PO-OMe)PdF(lut) (2, PO-OMe = P(2-OMe-Ph)2(2-SO3-5-Me-Ph), lut = 2,6-lutidine) and its reactions with electron-deficient olefins are described. The reaction of (PO-OMe)PdBr(lut) (1) with AgF affords 2 as an 82:18 mixture of cis-P,F and trans-P,F isomers. 2 isomerizes to a 1:2 cis-P,F:trans-P,F equilibrium mixture in CD2Cl2 solution at room temperature in ca. 3 days. 2 reacts with vinyl fluoride (VF) to afford (PO-OMe)Pd(CH2CHF2)(lut) (3), which exists as the cis-P,C isomer. 2 reacts with vinyl bromide (VBr) to yield 1 and VF by initial fluoropalladation to form (PO-OMe)Pd(CH2CHBrF)(lut) (4, not observed) followed by β-Br elimination. 2 reacts with vinyl acetate to yield (PO-OMe)Pd{CH2CHF(OAc)}(lut) (5), which reacts further to form the C-bound enolate complex (PO-OMe)Pd{CH2C(═O)H}(lut) (6) and acetyl fluoride. 2 reacts with vinyl benzoate in an analogous fashion. DFT analysis of the reaction of the model complexes cis-P,F- and trans-P,F...