Achieving High Ortho Selectivity in Aniline C-H Borylations by Modifying Boron Substituents

ACS Catalysis
Milton R SmithBuddhadeb Chattopadhyay

Abstract

High ortho selectivity for Ir-catalyzed C-H borylations (CHBs) of anilines results when B2eg2 (eg = ethylene glycolate) is used as the borylating reagent in lieu of B2pin2, which is known to give isomeric mixtures with anilines lacking a blocking group at the 4-position. With this modification, high selectivities and good yields are now possible for various anilines, including those with groups at the 2- and 3-positions. Experiments indicate that ArylN(H)Beg species are generated prior to CHB and support the improved ortho selectivity relative to B2pin2 reactions arising from smaller Beg ligands on the Ir catalyst. The lowest-energy transition states (TSs) from density functional theory computational analyses have N-H···O hydrogen-bonding interactions between PhN(H)Beg and O atoms in Beg ligands. Ir-catalyzed CHB of PhN(H)Me with B2eg2 is also highly ortho-selective. 1H NMR experiments show that N-borylation fully generates PhN(Me)Beg prior to CHB. The TS with the lowest Gibbs energy was the ortho TS, in which the Beg unit is oriented anti to the bipyridine ligand.

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Citations

Aug 29, 2019·Angewandte Chemie·Saqib A IqbalMichael J Ingleson
May 21, 2020·Organic & Biomolecular Chemistry·Yoichiro Kuninobu, Takeru Torigoe
Mar 1, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Jagadeesh Kalepu, Lukasz T Pilarski
Jun 27, 2019·Angewandte Chemie·Shao-Tao BaiJoost N H Reek
Mar 31, 2021·Journal of the American Chemical Society·Md Emdadul HoqueBuddhadeb Chattopadhyay
Jul 22, 2021·Chemistry : a European Journal·Clément JacobGwilherm Evano
Aug 7, 2019·Journal of the American Chemical Society·Madalina T MihaiRobert J Phipps
Jul 1, 2020·Journal of the American Chemical Society·Ya-Ming TianTodd B Marder
Nov 3, 2021·The Journal of Organic Chemistry·Chong LiuMing Lei
Nov 17, 2021·Chemical Communications : Chem Comm·Chabush HaldarBuddhadeb Chattopadhyay

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