Phosphorus Ligands from the Zhang Lab: Design, Asymmetric Hydrogenation, and Industrial Applications
Feng Wan and Wenjun Tang*
Chin. J. Chem. 2021, 39, 954—968. DOI: 10.1002/cjoc.202000605
Summary
Chiral phosphorus ligands have played a crucial role for the recent advances in asymmetric catalysis. This review summarizes chiral phosphorus ligands developed from the Laboratory of Professor Xumu Zhang in the latest 25 years. A number of iconic phosphorus ligands including bisphosphorus ligands with rigid chiral backbone such as BICP, PennPhos, TunePhos, and f-Binaphane, P-chiral bisphosphorus ligands TangPhos, Binapine, and DuanPhos, phosphine-phosphoramidte ligand YanPhos, noncovalent interaction-as-sisted ferrocenyl phosphorus ligand ZhaoPhos and WudaPhos, and tridentate ferrocenyl phosphorus ligands f-amphox are introduced, and their applications in asymmetric hydrogenation are emphasized.
手性膦配體在不對(duì)稱催化領(lǐng)域的發(fā)展中一直扮演著舉足輕重的角色。手性膦配體不僅決定了過渡金屬催化劑的手性環(huán)境,而且還調(diào)控著過渡金屬催化劑的電子和空間性能,因此直接影響了不對(duì)稱催化反應(yīng)的立體選擇性和反應(yīng)活性。自從上世紀(jì)70年代Knowles發(fā)展CAMP和DIPAMP并首次將不對(duì)稱氫化應(yīng)用于L-多巴的工業(yè)化生產(chǎn)以來,化學(xué)家們就從未停止對(duì)研究新型手性膦配體尤其是發(fā)展具有原創(chuàng)性結(jié)構(gòu)膦配體的腳步。
不對(duì)稱氫化是合成手性藥物最理想的反應(yīng)類型之一,但要實(shí)現(xiàn)完美的工業(yè)化過程,不對(duì)稱氫化反應(yīng)必須具有非凡的轉(zhuǎn)化數(shù)和優(yōu)秀的立體選擇性。張緒穆教授課題組一直致力于發(fā)展具有原創(chuàng)性結(jié)構(gòu)的手性膦配體,力爭(zhēng)實(shí)現(xiàn)具有工業(yè)應(yīng)用價(jià)值的高轉(zhuǎn)化數(shù)和立體選擇性,挑戰(zhàn)不對(duì)稱氫化領(lǐng)域中難以達(dá)到的高度,實(shí)現(xiàn)系列不對(duì)稱氫化反應(yīng)的工業(yè)化應(yīng)用。
在過去的25年中張緒穆教授課題組設(shè)計(jì)并發(fā)展了許多標(biāo)志性的優(yōu)勢(shì)膦配體,如骨架手性的雙膦配體(BICP,PennPhos,TunePhos,f-Binaphane),P手性雙膦配體(TangPhos,DuanPhos,Binapine)、磷-亞磷酰胺配體(YanPhos)、具有非共價(jià)相互作用輔助的二茂鐵磷配體(ZhaoPhos、WudaPhos、SPO-WudaPhos)以及三齒二茂鐵配體(f-amphox、f-amphol、f-ampha、f-amphamide)等。利用這些功能強(qiáng)大的手性膦配體,張緒穆教授課題組發(fā)展了多類不對(duì)稱氫化反應(yīng),實(shí)現(xiàn)了許多具有挑戰(zhàn)性的不對(duì)稱氫化轉(zhuǎn)化,獲得優(yōu)秀的對(duì)映選擇性和轉(zhuǎn)化數(shù)。許多不對(duì)稱氫化反應(yīng)已經(jīng)成功應(yīng)用于藥物或者關(guān)鍵藥物中間體的工業(yè)化制備中。本文綜述了張緒穆教授課題組在過去的25年中發(fā)展的系列重要手性膦配體,著重介紹這些配體結(jié)構(gòu)的設(shè)計(jì),不對(duì)稱氫化應(yīng)用范圍,以及它們的工業(yè)化實(shí)例。
本欄目已發(fā)表論文
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