Process for preparing ligands of the formula (1),
in which
R1 is C1-C8-alkyl, unsubstituted cyclopentyl, cyclohexyl, norbornyl or adamantyl, or cyclopentyl or cyclohexyl, substituted by 1 to 3 C1-C4-alkyl or C1-C4-alkoxy, or benzyl, phenyl, naphthyl and anthryl which are unsubstituted or substituted by 1 to 3 C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl or C1-C4-fluoroalkoxy, F and Cl,
each of R2 and R3 is independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and
R4 is C1-C4-alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl,
which comprises (a) stereoselective metallation in ortho position to the amine side-chain of a compound of formula (A)
in which R4 is as defined above,
reaction with a dihalide of formula R1-PX2 in which R1 is as defined above and X is Cl or Br, stereoselective hydrolysis to give a compound containing an SPO group, and reaction with a secondary phosphine of formula H-PR2R3 in which R2 and R3 are as defined above, to give the compounds of formula (1).
New ligands obtained by that process and metal complexes thereof.
制备式(1)
配体的工艺、
其中
R1 是 C1-C8- 烷基、未取代的环戊基、
环己基、降
冰片基或
金刚烷基,或被 1 至 3 个 C1-C4- 烷基或 C1-C4- 烷
氧基取代的环戊基或
环己基,或未取代或被 1 至 3 个 C1-C4- 烷基、C1-C4-烷
氧基、C1-C4-
氟烷基或 C1-C4-
氟烷氧基、F 和 Cl 取代的
苄基、
苯基、
萘基和
蒽基、
R2 和 R3 各自独立地是一个 C 键烃基或一个杂烃基,以及
R4 是 C1-C4 烷基、环戊基、
环己基、
苯基、
甲基苯基、
甲基苄基或
苄基、
其中包括 (a) 在式 (A) 化合物胺侧链的正交位置进行立体选择性
金属化
其中 R4 如上定义、
与式 R1-PX2 的二卤化物(其中 R1 如上定义,X 为 Cl 或 Br)反应,立体选择性
水解,得到含有
SPO 基团的化合物,再与式 H-PR2R3 的仲膦反应(其中 R2 和 R3 如上定义),得到式(1)化合物。
通过该工艺得到的新
配体及其
金属配合物。