Regioselective palladium(II)-catalyzed synthesis of five- or seven-membered ring lactones and five-, six- or seven-membered ring lactams by cyclocarbonylation methodology
Regioselective palladium(II)-catalyzed synthesis of five- or seven-membered ring lactones and five-, six- or seven-membered ring lactams by cyclocarbonylation methodology
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DOI：
10.1021/ja953403l
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发表时间：
1996-05-08
影响因子：
15
通讯作者：
Alper, H
中科院分区：
文献类型：
--
作者：
ElAli, B;Okuro, K;Alper, H
2-烯丙基苯酚与一氧化碳和氢气在催化量的阳离子钯（II）配合物[（PCy（3））（2）Pd（H）（H2O）]（BF 4-）-B-+或乙酸钯和1，4-双（二苯基膦基）丁烷存在下反应，得到五元或七元环内酯（双环、三环和五环）作为主要产物，通常产率很高。使用2-氨基苯乙烯作为反应物和催化量的乙酸钯和三环己基膦，以高产率和选择性提供五元环内酰胺。以2-烯丙基苯胺为原料，在Pd（OAc）（2）/PPh（3）催化体系下，与CO/H2反应，合成了含六元环内酰胺的双环和三环杂环化合物。在后一种方法中用（二苯基膦基）丁烷代替PPh（3）导致以良好的产率形成七元内酰胺苯并氮杂卓酮，区域化学控制取决于钯催化剂的性质、气体的相对压力和溶剂。
2-Allylphenols react with carbon monoxide and hydrogen in the presence of catalytic quantities of a cationic palladium(II) complex [(PCy(3))(2)Pd(H)(H2O)](BF4-)-B-+ or palladium acetate and 1,4-bis(diphenylphosphino)butane, affording five- or seven-membered ring lactones (bicyclic, tricyclic, and pentacyclic) as the principal products, often in excellent yields. Use of 2-aminostyrenes as reactants and catalytic quantities of palladium acetate and tricyclohexylphosphine, affords five-membered ring lactams in high yield and selectivity. Bicyclic and tricyclic heterocycles containing six-membered ring lactams can be synthesized from the reaction of 2-allylanilines with CO/ H-2 using the catalytic system Pd(OAc)(2)/PPh(3), while use of 1,4-bis(diphenylphosphino)butane instead of PPh(3) in the latter process results in the formation of the seven-membered lactams benzazepinones in good yield, The regiochemical control depends on the nature of the palladium catalyst, the relative pressures of the gases, and the solvent.