Rhodium‐Catalyzed P^III‐Directed ortho‐C−H Borylation of Arylphosphines

Abstract

Transition-metal-mediated metalation of an aromatic C À Hbond that is adjacent to atertiary phosphine group in arylphosphines via af our-membered chelate ring was first discovered in 1968. Herein, we overcome al ong-standing problem with the ortho-CÀHa ctivation of arylphosphines in ac atalytic fashion. In particular,w ed eveloped ar hodiumcatalyzedo rtho-selective C À Hb orylation of various commercially available arylphosphines with B 2 pin 2 through P IIIchelation-assisted CÀHactivation. This discovery is suggestive of ag eneric platform that could enable the late-stage modification of readily accessible arylphosphines.

External oxidant-compatible phosphorus(III)-directed site-selective C–H carbonylation

“…1A, left) (10)(11)(12)(13)(14). Recently, phosphorus(III)-chelation assisted C-H functionalization has been disclosed with transition metal cataly sis, but external oxidants cannot be used in these reactions (15)(16)(17)(18)(19)(20)(21)(22). P(III) functional groups are usually unstable in the presence of oxi dants due to the ease of forming P(V) species, (23) thus limiting the applicability of this chemistry (Fig.…”

Remote Selective C−H Halogenation of Arylphosphine Oxides with Ferric Halides

“…[1] During the last decade, one of the most important approaches for the construction of functionalized phosphorus-containing compounds is metalcatalyzed CÀ H functionalization reactions of arylphosphines and arylphosphine oxides (Figure 1). [2][3][4][5][6][7][8] In general, the directing PR 2 or P(O)R 2 group via four-, five-, or six-membered metallacycle intermediates to afford ortho-or ortho'-functionalized products in the presence of metal catalyst. [2,3,5,6,7] Moreover, monophosphino-o-carboranes could undergo B3À H, B6À H, or CÀ H functionalization using Rh(I) or Pd(II) catalysis.…”

“…[2][3][4][5][6][7][8] In general, the directing PR 2 or P(O)R 2 group via four-, five-, or six-membered metallacycle intermediates to afford ortho-or ortho'-functionalized products in the presence of metal catalyst. [2,3,5,6,7] Moreover, monophosphino-o-carboranes could undergo B3À H, B6À H, or CÀ H functionalization using Rh(I) or Pd(II) catalysis. [8] Shi's group found metal-catalyzed direct functionalization of indoles at C6 or C7 positions using NÀ P(O)(tBu) 2 or NÀ P(tBu) 2 as a directing group.…”