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A Photosensitizing Metal–Organic Framework as a Tandem Reaction Catalyst for Primary Alcohols from Terminal Alkenes and Alkynes

Xiao‐Chun Lin, Yumei Wang, Xu Chen, Pei‐Ye You, Kai‐Ming Mo, Guo‐Hong Ning, Dan Li

2023Angewandte Chemie International Edition86 citationsDOI

Abstract

Owing to the wide and growing demand for primary alcohols, the development of efficient catalysts with high regioselectivity remains a worthwhile pursuit. However, according to Markovnikov's rule, it is a challenge to obtain primary alcohols with high yields and regioselectivity from terminal alkenes or alkynes. Herein, we report the synthesis of a photosensitizing two-dimensional (2D) metal-organic framework (MOF) from cyclic trinuclear copper(I) units (Cu-CTUs) and a boron dipyrro-methene (Bodipy) ligand. The MOF features broadband light absorption, excellent photoinduced charge separation efficiency, and photochemical properties. By integrating the copper-catalyzed hydroboration and photocatalyzed aerobic oxidation, it can catalyze terminal alkenes and alkynes to produce primary alcohols via a one-pot tandem reaction with excellent regioselectivity, good overall yields in two-step reactions (up to 85 %), broad substrate compatibility (32 examples) and good reusability under mild conditions.

Topics & Concepts

RegioselectivityHydroborationChemistryCatalysisMarkovnikov's ruleTandemCombinatorial chemistryOrganic synthesisPrimary (astronomy)Photoredox catalysisOrganic chemistryAlcohol oxidationCopperPhotochemistryPhotocatalysisMaterials scienceAstronomyComposite materialPhysicsMetal-Organic Frameworks: Synthesis and ApplicationsCovalent Organic Framework ApplicationsAdvanced Photocatalysis Techniques