Copper(I) Complexes of P -Stereogenic Josiphos and Related Ligands
Copper(I) Complexes of P -Stereogenic Josiphos and Related Ligands
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P-立构 Josiphos 的铜 (I) 配合物及相关配体
DOI：
10.1002/ejoc.202100146
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发表时间：
2021
影响因子：
2.8
通讯作者：
Arthurs R
中科院分区：
文献类型：
--
作者：
Arthurs R
从（R）-Ugi胺开始，非对映选择性锂化，然后是Ar'PCl 2，然后是Ar“MgBr，导致作为单一非对映异构体的（R，Sp，Sphos）[Ar”= Ph，Ar“= o-Tol]和（R，Sp，Rphos）[Ar”= o-Tol，Ar“=Ph] PPFA配体衍生物的产生。用HPCy 2进行胺取代，得到P-立体异构Josiphos配体，然后加入CuCl，得到相应的铜（I）配合物。后者也通过使用硼烷P和N保护基和原位Cu（I）络合来生成，避免了分离空气敏感的膦中间体。 这种保护方法也适用于合成Josiphos/CuCl络合物衍生自PCl 3。此外，还获得了相关的基于大体积钴夹心络合物的衍生物。初步调查显示，分离的CuCl络合物作为主管催化剂前体的对映选择性共轭加成反应。
Starting from (R)‐Ugi's amine, diastereoselective lithiation followed by Ar'PCl2and then Ar’’MgBr led to the generation, as single diastereoisomers, of (R,Sp,Sphos) [Ar’=Ph, Ar’’=o‐Tol] and (R,Sp,Rphos) [Ar’=o‐Tol, Ar’’=Ph] PPFA ligand derivatives. Amine substitution of both with HPCy2gaveP‐stereogenic Josiphos ligands, and then addition of CuCl, the corresponding copper(I) complexes. The latter were also generated by using borane P and N protecting groups andin situCu(I) complexation, avoiding the isolation of air‐sensitive phosphine intermediates. This protection methodology was also applied to the synthesis of Josiphos/CuCl complexes derived from PCl3. In addition, related bulky cobalt‐sandwich complex‐based derivatives were also obtained. Preliminary investigation revealed isolated CuCl complexes as competent catalyst precursors for enantioselective conjugate addition reactions.