当前位置: X-MOL 学术Inorg. Chem. Front. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Hydrogenation reactions catalyzed by HN(CH2CH2PR2)2-ligated copper complexes
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2021-08-30 , DOI: 10.1039/d1qi00776a
Dewmi A. Ekanayake 1 , Arundhoti Chakraborty 1 , Jeanette A. Krause 1 , Hairong Guan 1
Affiliation  

HN(CH2CH2PR2)2-ligated copper borohydride complexes, (RPNHP)Cu(BH4) (R = iPr, Cy, tBu), which can be prepared from (RPNHP)CuBr and NaBH4, are capable of catalyzing the hydrogenation of aldehydes in an alcoholic solvent. More active hydrogenation catalysts are (RPNHP)CuBr mixed with KOtBu, allowing various aldehydes and ketones to be efficiently reduced to alcohols except those bearing a nitro, N-unprotected pyrrole, pyridine, or an ester group, or those prone to aldol condensation (e.g., 1-heptanal). Modifying the catalyst structure by replacing the NH group in (iPrPNHP)CuBr with an NMe group results in an inferior catalyst but preserves some catalytic activity. The hexanuclear copper hydride cluster, (iPrPNHP)3Cu6H6, is also competent in catalyzing the hydrogenation of aldehydes such as benzaldehyde and N-methyl-2-pyrrolecarboxaldehyde, albeit accompanied by decomposition pathways. The catalytic performance can be enhanced through the addition of a strong base or iPrPNHP. The three catalytic systems likely share the same catalytically active species, which is proposed to be a mononuclear copper hydride (RPNHP)CuH with the NH group bound to copper.

中文翻译:

HN(CH2CH2PR2)2-连接的铜配合物催化的氢化反应

HN(CH 2 CH 2 PR 22 -ligated硼氢化铜配合物,(- [R PN ħ P)的Cu(BH 4)(R =镨中,Cy,丁基),其可从制备(- [R PN ħ P) CuBr 和 NaBH 4能够在醇溶剂中催化醛的氢化。更活泼的加氢催化剂是 ( R PN H P)CuBr 与 KO t Bu混合,可以将各种醛和酮有效地还原为醇,除了那些带有硝基、N-未保护的吡咯、吡啶或酯基,或那些易于醛醇缩合的基团(例如,1-庚醛)。通过更换NH基在(改性催化剂结构PN ħ与较差的催化剂的NME组的结果,但蜜饯一些催化活性P)的CuBr。的六核氢化铜簇,(PN ħ P)3的Cu 6 ħ 6,也就是在催化醛如苯甲醛和加氢主管Ñ甲基-2- pyrrolecarboxaldehyde,虽然伴随着分解途径。催化性能可以通过添加强碱或PN ħ P.三个催化体系可能共享相同的催化活性物质,其被提议为单核氢化铜( ř PN ħ P)CUH与结合到铜的NH基团。
更新日期:2021-09-08
down
wechat
bug