Recent advances in photochemical construction of aromatic C–P bonds via C–hetero bond cleavage

Abstract

Photochemical C–P bond cross-coupling in aromatics via C–X (X = F, Cl, Br, I), C–N bond and C–O bond cleavages with/without photosensitizer were summarized in this review.

Site-selective and metal-free C–H phosphonation of arenes via photoactivation of thianthrenium salts

“…In this eld, photo-, 5 metallaphotoredox 6 and electron-donor-acceptor (EDA) methods 7 (Scheme 1A) have been employed using different aryl radical precursors, such as aryl halides, aminated arenes, or aryl sulfonates through homolytic cleavage of C(sp 2 )heteroatom bonds. 8 In addition, two examples of light induced direct C(sp 2 )-H phosphonation have been reported in the same year. One of them, developed by König functionalizes electronrich arenes by means of a ruthenium photocatalyst in combination with ammonium persulfate as sacricial oxidant, 9 while the second reported by Lei group uses a dual catalytic system composed of acridinium photosensitiser and a Co co-catalyst.…”

“…A range of 2-substituted anisoles were amenable to this transformation, obtaining 2-nitrile (4), 2-halogenated (5 and 6) and 2-aldehyde (7) derivatives in high yields. Arenes containing alkylated substitutions were also competent substrates (8)(9)(10), yielding the desired aryl phosphonates from moderate to good yields. Biphenyls were used as coupling partners with success including biphenyl (11) and 4-bromophenyl (12), which the presence of the bromide allows subsequent postfunctionalization.…”

Highly efficient and well-defined phosphinous acid-ligated Pd(ii) precatalysts for Hirao cross-coupling reaction

“…13,[17][18][19][20][21][22] With the aid of microwave apparatus, Keglevich et al reported catalyst-free, 23 ligand-free 24 and ligand-free/ solvent-free 25,26 conditions for coupling C SP 2-P(vO) bonds. In addition to a recently developed photocatalyst-free (transitionmetal-free) method for making valuable organophosphorus compounds, 27 importantly, Montchamp et al demonstrated that the C SP 2-P(vO) coupling of 2-chloropyrazine was successfully catalysed by 1 mol% of an in situ Pd(OAc) 2 /dppf catalytic system. 28 It is also noteworthy that Herzon and co-workers showed that the coupling of secondary phosphine oxides (SPOs) and aryl iodides could be catalysed at room temperature by Pd 2 dba 3 /Xantphos (0.5 mol%/1 mol%).…”

Radical Phosphorylation of Aliphatic C–H Bonds via Iron Photocatalysis

“…In recent years, radical phosphorylation has emerged as a powerful platform for the construction of tertiary phosphines (Scheme b). − The first radical phosphorylation of organic halides and alkyl imidazole-1-carbothioate with chlorodiphenylphosphine has been exploited by Oshima and Yorimitsu et al in boiling benzene . By employing Me 3 SnPPh 2 as a P-source, Studer and Curran et al.…”