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Abstract N- Arylation of NH -sulfoximines represents an appealing approach to access N- aryl sulfoximines, but has not been successfully applied to NH -diaryl sulfoximines. Herein, a copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids is described. This neutral and ligand-free coupling is initiated by ambient light-induced copper-catalyzed single-electron reduction of NH -sulfoximines. This electron transfer route circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions, increasing the environmental friendliness of this process. Instead, dihydrogen gas forms as a byproduct of this reaction. Mechanistic investigations also reveal a unique autocatalysis process. The C–N coupling products, N- arylated sulfoximines, serve as ligands along with NH -sulfoximine to bind to the copper species, generating the photocatalyst. DFT calculations reveal that both the NH -sulfoximine substrate and the N -aryl product can ligate the copper accounting for the observed autocatalysis. Two energetically viable stepwise pathways were located wherein the copper facilitates hydrogen atom abstraction from the NH -sulfoximine and the ethanol solvent to produce dihydrogen. The protocol described herein represents an appealing alternative strategy to the classic oxidative Chan-Lam reaction, allowing greater substrate generality as well as the elimination of byproduct formation from oxidants. 

Reactions of (O=)PH(OCH₂CH₃)₂and BrMg(CH₂)_mCH=CH₂(4.9–3.2 equiv;m=4 (a), 5 (b), 6 (c)) give the dialkylphosphine oxides (O=)PH[(CH₂)_mCH=CH₂]₂(2 a–c; 77–81 % after workup), which are treated with NaH and then α,ω‐dibromides Br(CH₂)_nBr (0.49–0.32 equiv;n=8 (a′), 10 (b′), 12 (c′), 14 (d′)) to yield the bis(trialkylphosphine oxides) [H₂C=CH(CH₂)_m]₂P(=O)(CH₂)_n(O=)P[(CH₂)_mCH=CH₂]₂(3 ab′,3 bc′,3 cd′,3 ca′; 79–84 %). Reactions of3 bc′and3 ca′with Grubbs’ first‐generation catalyst and then H₂/PtO₂afford the dibridgehead diphosphine dioxides(4 bc′,4 ca′; 14–19 %,n′=2m+2);³¹P NMR spectra show two stereoisomeric species (ca. 70:30). Crystal structures of two isomers of the latter are obtained,out,out‐4 ca′and a conformer ofin,out‐4 ca′that features crossed chains, such that the (O=)P vectors appearout,out. Whereas4 bc′resists crystallization, a byproduct derived from an alternative metathesis mode, (CH₂)₁₂P(=O)(CH₂)₁₂(O=)P(CH₂)₁₂, as well as3 ab′and3 bc′, are structurally characterized. The efficiencies of other routes to dibridgehead diphosphorus compounds are compared.