School of Chemistry and Chemical Engineering, Henan Normal University, Pingyuan Laboratory, Xinxiang, Henan, 453007, P. R. China.
International Scientific and Technological Cooperation Base of Chiral Chemistry, Henan University, Kaifeng, Henan, 475004, P. R. China.
Angew Chem Int Ed Engl. 2023 Apr 11;62(16):e202216605. doi: 10.1002/anie.202216605. Epub 2023 Mar 13.
A chiral Brønsted acid-catalysed asymmetric hydrophosphinylation of 2-vinylazaarenes by secondary phosphine oxides is described. A variety of P-chiral 2-azaaryl-ethylphosphine oxides are synthesized with high yields and ees, of which both the substituents of phosphines and azaarenes can be flexibly modulated, underscoring an exceptionally broad scope of substrates. These adducts are valuable to asymmetric metal catalysis since the resultant P-chiral tertiary phosphines from the reduction of them are verified as a kind of effective C -symmetric chiral 1,5-hybrid P,N-ligands. Importantly, this catalysis platform enables the generic and efficient kinetic resolution of P-chiral secondary phosphine oxides. It thus provides an expedient approach to access the enantiomers of the P-chiral tertiary phosphine oxides derived from asymmetric hydrophosphinylation, further improving the utility of the method.
本文描述了一种通过二级膦氧化物对 2-乙烯基氮杂芳烃的手性 Brønsted 酸催化不对称氢膦化反应。通过该方法，以高产率和高对映选择性合成了多种 P-手性 2-氮杂芳基乙基膦氧化物，其中膦和氮杂芳烃的取代基都可以灵活调节，这突出了底物具有非常广泛的范围。这些加成物对于不对称金属催化很有价值，因为通过还原得到的 P-手性叔膦被证明是一种有效的 C-对称手性 1,5-混合 P,N-配体。重要的是，该催化平台可以实现 P-手性二级膦氧化物的通用和高效动力学拆分。因此，它为通过不对称氢膦化反应获得的 P-手性叔膦氧化物的对映异构体提供了一种便捷的方法，进一步提高了该方法的实用性。
