A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion

Zhao, Jie; Ji, Shufang; Guo, Chenxi; Li, Haijing; Dong, Juncai; Guo, Ping; Wang, Dingsheng; Li, Yadong; Toste, F. Dean

doi:10.1038/s41929-021-00637-7

A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion

Journal Article · Mon Jun 21 00:00:00 EDT 2021 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-021-00637-7· OSTI ID:1839015

^[1]; Ji, Shufang ^[2]; Guo, Chenxi ^[3]; Li, Haijing ^[4]; ^[4]; Guo, Ping ^[1]; ^[2]; ^[2]; ^[5]

East China Univ. of Science and Technology, Shanghai (China). Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Key Lab. for Advanced Materials, Joint International Research Lab. of Precision Chemistry and Molecular Engineering
Tsinghua Univ., Beijing (China)
Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics, State Key Lab. of Catalysis
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics (IHEP), Beijing Synchrotron Radiation Facility
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C–O bonds. Achieving site-selective functionalization of alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report a strategy for selective carbenoid O–H insertion that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities for organic transformations by merging material science and catalysis. This catalytic protocol delivers excellent selectivities (up to 99:1) for the functionalization of aliphatic over phenolic O–H bonds, whereas the analogous homogeneous catalyst, Ir(ttp)COCl (ttp = 5,10,15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest that the site-selectivity derives from the lower oxidation state of the iridium metal centre in the heterogeneous catalyst and its impact on the absorption energies of the reactants. These results showcase an example of a heterogeneous single-atom catalyst providing superior site-selectivity and provide a complementary strategy to address challenges in catalysis for organic synthesis. [Figure not available: see fulltext.]

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Key R&D Program of China; National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1839015

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 6 Vol. 4; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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