The palladium diphosphinoboryl pincer [{(o-PPhCH)B}PdI] 8 was prepared from the diphosphinoborane complex 6a. The boryl functionality of the pincer displayed ambiphilic properties allowing: (1) coordination of Lewis basic pyridines to the boryl site and (2) access to palladium diphosphinoborane complex derivatives.
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http://dx.doi.org/10.1039/c6cc07079e | DOI Listing |
J Am Chem Soc
December 2024
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
Functional group-directed site- and enantioselective C(sp)-H functionalization of alcohols or masked alcohols represents a formidable challenge. We herein report the first example of iridium-catalyzed asymmetric α-C(sp)-H borylation of primary alcohol-derived carbamates by the judicious choice of directing groups. A variety of chiral borylated carbamates were obtained with good to high enantioselectivities.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China.
Angew Chem Int Ed Engl
December 2024
Max Planck Institute of Colloids and Interfaces: Max-Planck-Institut fur Kolloid und Grenzflachenforschung, Biomolecular Sytems, Am Mühlenberg 1, 14476, Potsdam, GERMANY.
Energy transfer catalysis (EnT) has had a profound impact on contemporary organic synthesis enabling the construction of higher in energy, complex molecules, via efficient access to the triplet excited state. Despite this, intermolecular reactivity, and the unique possibility to access several reaction pathways via a central triplet diradical has rendered control over reaction outcomes, an intractable challenge. Extended chromophores such as non-symmetrical dienes have the potential to undergo [2+2] cycloaddition, [4+2] cycloaddition or geometric isomerisation, which, in combination with other mechanistic considerations (site- and regioselectivity), results in chemical reactions that are challenging to regulate.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
State Key Laboratory of Medical Chemical Biology and College of Pharmacy, Nankai University, Tianjin 300071, P. R. China.
Compounds bearing both boryl and amino groups at distal positions are invaluable synthons for synthesizing pharmaceuticals, drug candidates, and natural products, but their catalytic enantioselective synthesis remains rarely explored. We report the first enantioselective 1,4-borylamination reaction through a copper-catalyzed cascade hydroborylation and hydroamination of arylidenecyclopropanes. This reaction combines four readily available components in a highly chemo-, site-, and enantioselective fashion (>20:1 r.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, Indian Institute of Technology Delhi Hauz Khas, New Delhi, 110016, India.
We report the development of an earth-abundant metal catalyst for methane C-H borylation. The post-synthetic metalation of bipyridine-functionalized zirconium metal-organic framework (MOF) with NiBr, followed by treatment with NaEtBH affords MOF-supported monomeric bipyridyl-nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 °C using pinacolborane (HBpin) to afford CHBpin in 61 % yield with a turnover number (TON) up to 1388.
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