温和条件下P(V)促进的铑催化苯乙烯的高区域选择性氢甲酰化反应

Ru Tong, Zhang Yajiao, Wei Qiuxiang, Zuo Sheng, Jia Zhenhua, Chen Fen-Er

Department of Medicinal Chemistry, School of Pharmacy, Fudan University, Shanghai 201203, China.

Engineering Center of Catalysis and Synthesis for Chiral Molecules, Department of Chemistry, Fudan University, Shanghai 200433, China.

Molecules. 2024 Apr 28;29(9):2039. doi: 10.3390/molecules29092039.

Hydroformylation of olefins is widely used in the chemical industry due to its versatility and the ability to produce valuable aldehydes with 100% atom economy. Herein, a hybrid phosphate promoter was found to efficiently promote rhodium-catalyzed hydroformylation of styrenes under remarkably mild conditions with high regioselectivities. Preliminary mechanistic studies revealed that the weak coordination between the Rhodium and the P=O double bond of this pentavalent phosphate likely induced exceptional reactivity and high ratios of branched aldehydes to linear products.

由于烯烃氢甲酰化反应具有多功能性且能够以100%的原子经济性生产有价值的醛类化合物，因此该反应在化学工业中得到了广泛应用。在此，人们发现一种混合磷酸盐促进剂能够在非常温和的条件下高效促进铑催化的苯乙烯氢甲酰化反应，并具有高区域选择性。初步机理研究表明，铑与这种五价磷酸盐的P=O双键之间的弱配位可能导致了异常的反应活性以及高比例的支链醛与线性产物。