Palladium-catalyzed synthesis of 1-alkylphosphonium salts from 1-alkenes.
Palladium-catalyzed synthesis of 1-alkylphosphonium salts from 1-alkenes.
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DOI：
10.1002/chin.200621174
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发表时间：
2006-01
影响因子：
15
通讯作者：
M. Arisawa;M. Yamaguchi
中科院分区：
文献类型：
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作者：
M. Arisawa;M. Yamaguchi
钯（0）络合物催化三芳基膦和质子酸与1-烯烃的加成反应，得到1-烷基鏻盐。在Pd 2（dba）3·CHCl 3（dba =二亚苄基丙酮）（0.1mol%）存在下，在氯苯中于65 ℃下将常压乙烯、三苯基膦和（CF 3SO 2）2NH处理5小时，以98%的分离产率得到乙基鏻盐。以常压丙烯为原料，合成了反马氏加成物1-丙基鏻盐，收率95%。1-在1摩尔%催化剂存在下，丁烯以92%的产率转化为1-丁基鏻盐。该反应与烯烃异构化竞争，并且回收2-丁烯和1-丁烯的混合物（>20：1）。1-戊烯和1-己烯与三苯基膦的反应得到中等产率的产物。然而，反应性较低的1-烯烃与三（对氯苯基）膦有效反应。内烯烃、2-和3-戊烯也通过快速烯烃迁移以高产率得到1-戊基鏻盐。
A palladium(0) complex catalyzes the addition reaction of a triarylphosphine and a protic acid to a 1-alkene, giving a 1-alkylphosphonium salt. The treatment of atmospheric ethylene, triphenylphosphine, and (CF3SO2)2NH in the presence of Pd2(dba)3.CHCl3 (dba = dibenzylideneacetone) (0.1 mol %) in chlorobenzene at 65 degrees C for 5 h gave ethylphosphonium salt in 98% isolated yield. The anti-Markovnikov adduct 1-propylphosphonium salt was obtained by the reaction of atmospheric propene in 95% yield. 1-Butene was converted to 1-butylphosphonium salt in 92% yield in the presence of 1 mol % catalyst. This reaction competed with olefin isomerization, and a mixture of 2-butene and 1-butene (>20:1) was recovered. The reactions of 1-pentene and 1-hexene with triphenylphosphine gave modest yields of the products. The less reactive 1-alkenes, however, reacted effectively with tris(p-chlorophenyl)phosphine. The inner olefins, 2- and 3-pentene also gave a 1-pentylphosphonium salt in high yields via rapid olefin migration.