PALLADIUM-CATALYZED ADDITIONS OF AMINES TO CONJUGATED DIENES - ALTERATION OF BEHAVIOR OF (TRIPHENYLPHOSPHINE)PALLADIUM CATALYSTS WITH AMINE HYDROIODIDE SALTS
PALLADIUM-CATALYZED ADDITIONS OF AMINES TO CONJUGATED DIENES - ALTERATION OF BEHAVIOR OF (TRIPHENYLPHOSPHINE)PALLADIUM CATALYSTS WITH AMINE HYDROIODIDE SALTS
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DOI：
10.1021/om00133a011
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发表时间：
1986-02-01
期刊：
影响因子：
2.8
通讯作者：
DIECK, HA
中科院分区：
文献类型：
--
作者：
ARMBRUSTER, RW;MORGAN, MM;DIECK, HA
我们发现，在胺与共轭二烯的反应中，氢碘胺盐能够改变（三苯基膦）钯催化剂体系的行为。这种反应产生1:1加合物，在1,3 -丁二烯、异戊二烯和2,3 -二甲基- 1,3 -丁二烯的情况下，这些加合物主要由横跨二烯体系的NH部分的1,4加成所产生的产物组成。这些加成产物得到了相当好的产量，只有微量的1,2加成产物和辛二烯胺（1:1加合物）形成。文献报道了使用（三苯基膦）钯催化剂而不使用氢碘化胺盐的类似体系，表明八烯胺是主要产物。1,2 -辛二烯胺也是采用膦酸3,4和1,5 -环辛二烯基配体反应的主要产物。1 2345其他报告表明，当二膦配体，例如1,2 -二（二苯基膦）乙烷取代三苯基膦（无氢碘胺盐）时，得到1:1加合物6,7，但在某些情况下，产物(1)(a) Takahashi， S.；Shibano t;Hagihara， N.牛。化学。Soc。日刊，1968,41454。(b) Shryne， TM美国专利3530187,1970；化学。摘要：1970,73,930615。(c)沃克，WE；马尼克，r.m.；阿德金斯，k.e.；李建军，李建军，李建军，等。(d)哈塔，T.；高桥,k;Miyaki， A. Japan 72 25045, 1972；化学。摘要：1972,77,101117。(e)渡边，h；Nagai, a;斋藤,m;田中,h;Nagai， Y. Asaki Garasu Kogyo Gijutsu shorekai 1981,38, 111；化学。摘要：1982,97,181653。(f)凯姆，W.；鲁普,m;张志强，张志强。中国科学院学报，1993,19(3):444 - 444。(2)(a) Mitsuyasu, t；Hara m;Tsuji, j.j. Chem。Soc。D 1971, 1345。(b) Tsuji， J. Japan 7522014, 1975；化学。摘要：1975,84,16736。(3)(a)霍布斯，c.f.；McMackins， DEUS专利4100194,1978；化学。摘要：1979,90,22297。(b)霍布斯，c.f.；McMackins， DEUS专利4130590,1978；化学。摘要：1979,90,137247。(4)(a)霍布斯，c.f.；McMackins， DEUS专利4100196,1978；化学。摘要：1979,90,5894。(b)凯姆，W.；库尔茨，k.r.；李建平，李建平。中国科学。1993,19(2):1 - 3。
We have found that amine hydroiodide salts are capable of altering the behavior of (triphenylphosphine) palladium catalyst systems in reactions of amines with conjugated dienes. Such reactions produce 1: 1 adducts which, in the case of 1, 3-butadiene, isoprene, and 2, 3-dimethyl-l, 3-butadiene, consist primarily of products resulting from a 1, 4-addition of the NH moiety across the diene system. These addition products are obtained in fair to good yields with only traces of 1, 2-addition products and octadienyl amines (1: 2 adducts) being formed. Literature reports of similar systems using (triphenylphosphine) palladium catalysts without the amine hydroiodide salt indicate that octadienylamines are the major products. 1, 2 Octadieny-lamines are also the major products in reactions employing phosphonite3, 4 and 1, 5-cyclooctadienyl ligands. 1 2345 Other reports indicate that when a diphosphine ligand, eg, l, 2-bis (diphenylphosphino) ethane, is substituted for triphenylphosphine (no amine hydroiodide salt), 1: 1 ad-ducts are obtained, 6, 7 but in some cases the products (1)(a) Takahashi, S.; Shibano, T.; Hagihara, N. Bull. Chem. Soc. Jpn. 1968, 41,454.(b) Shryne, TM US Patent 3530187, 1970; Chem. Abstr. 1970, 73, 930615.(c) Walker, WE; Manyik, R. M.; Adkins, K. E.; Farmer, ML Tetrahedron Lett. 1970, 43, 3817.(d) Hata, T.; Takahashi, K.; Miyaki, A. Japan 72 25045, 1972; Chem. Abstr. 1972, 77, 101117.(e) Watanabe, H.; Nagai, A.; Saito, M.; Tanaka, H.; Nagai, Y. Asaki Garasu Kogyo Gijutsu Shoreikai 1981, 38, 111; Chem. Abstr. 1982, 97, 181653.(f) Keim, W.; Roeper, M.; Schieren, MJ Mol. Catal. 1983, 20, 139.(2)(a) Mitsuyasu, T.; Hara, M.; Tsuji, J. J. Chem. Soc. D 1971, 1345.(b) Tsuji, J. Japan 7522014, 1975; Chem. Abstr. 1975, 84, 16736.(3)(a) Hobbs, C. F.; McMackins, DEUS Patent 4100194, 1978; Chem. Abstr. 1979, 90, 22297.(b) Hobbs, C. F.; McMackins, DEUS Patent 4130590, 1978; Chem. Abstr. 1979, 90, 137247.(4)(a) Hobbs, C. F.; McMackins, DEUS Patent 4100196, 1978; Chem. Abstr. 1979, 90, 5894.(b) Keim, W.; Kurtz, K. R.; Roeper, MJ Mol. Catal. 1983, 20, 129.