Confined Trinuclear Ru Sites in Phosphine-Incorporated
Porous Organic Polymers for the Direct Synthesis of Alcohols from
Reductive Hydroformylation of Alkenes
posted on 2024-03-12, 16:49authored byYinghao Zhu, Zhaozhan Wang, Yuanjun Zhao, Xin Zhou, Yan Zhang, Yong Yang
Direct
conversion of readily available alkenes into high-value-added
alcohols is important yet challenging in both organic synthesis and
industry. One-pot reductive hydroformylation of alkenes offers a straightforward
and atom-economical method for the synthesis of one-carbon homologated
alcohols. However, the reaction catalyzed by a stable and efficient
heterogeneous catalyst has been underexplored. Herein, we report a
bench-stable porous organic polymer (POP) with incorporation of a
specific monophosphine ligand into the scaffold, which serves as both
a solid ligand and a support to prepare a heterogeneous Ru catalyst
for one-pot reductive hydroformylation. The monophosphine ligand helps
to stabilize atomically dispersed trinuclear Ru sites on POP, resulting
in a heterogeneous Ru catalyst with a catalytic performance comparable
to its homogeneous counterpart under the same conditions. The catalyst
could be easily separated for successive reuses without a significant
loss in both activity and selectivity. Remarkably, the catalyst exhibited
outstanding chemo- and regioselectivity, allowing for the efficient
conversion of a wide range of terminal, internal, and functional alkenes
to their respective alcohols in good to high yields. This work demonstrates
the use of atomically dispersed metal sites for the reductive hydroformylation
of alkenes for the direct synthesis of alcohols.