Highly Efficient Palladium-Catalyzed Arsination. Synthesis of a Biphenyl Arsine Ligand and Its Application to Obtain Perfluoroalkylarsines

Abstract

An efficient one-pot, two-step Pd-catalyzed arsination with n-Bu3SnAsPh2 (1) and sterically hindered aryl iodides (ArI) with different functional groups is reported. The cross-coupling reactions of this stannane with ArI afforded the functionalized triarylarsines in very good isolated yields (71−88%). By using this methodology, a biphenyl arsine ligand, AsPh2(bph), was achieved, and its use as ligand in the Pd-catalyzed arsination with RfI to obtain perfluoroalkylarsines is also reported. In this reaction, the activity of a variety of phosphine and arsine ligands was investigated. The new biphenyl arsine ligand AsPh2(bph) proved to be the best one for the arsination reaction with RfI.

Bulky Monodentate Biphenylarsine Ligands: Synthesis and Evaluation of Their Structure Effects in the Palladium‐Catalyzed Heck Reaction

“…The products were characterized by 1 H NMR, 13 C NMR, 31 P NMR, and 19 F NMR, 2D NMR, GC–MS, and HRMS. All the spectroscopic data agreed with those previously reported for compound L1 7b and for compounds L2 – L6 and L9 9…”

“…(2‐Bromophenyl)diphenylarsine ( 3 ) was employed as a synthetic intermediate for the synthesis of biarylarsine ligands. Arsination of the stannane n Bu 3 SnAsPh 2 ( 1 ) with 1‐bromo‐2‐iodobenzene ( 2 ), catalyzed by (PPh 3 ) 2 PdCl 2 in toluene, afforded the arsine 3 in 83 % isolated yield (Scheme ) 7b,9…”

“…DMF was stored under molecular sieves and then distilled under reduced pressure with bubbling of nitrogen. (2‐Bromophenyl)diphenylarsine ( 3 ) was prepared as previously reported, from the corresponding 2‐bromoiodobenzene 7b. 2‐Diphenylphosphino‐2′,6′‐dimethoxybiphenyl ( L10‐Phos ) was prepared by literature methods 37…”

Palladium-Mediated Organofluorine Chemistry

“…The use of other palladium sources (such [Pd(PPh 3 ) 4 ] or Pd 2 (dba) 3 ), or other phosphines as ligands led to worse results. 42,43 R F I + R 2 P-SnBu 3 [Pd] ER n = SePh, AsPh 2 R F I + R n E-SnBu 3 [Pd]…”

Synthesis and low-temperature dehydrating imidation polymerization of 1,4-dihydro-1,4-diarsininetetracarboxylic acid dianhydride

“…Among the various types of such polymers, much attention has been paid to heteroatomcontaining polyimides in attempts to develop high-performance functional polymers, such as high-refractive-index polymers for optical applications, polymers resistant to atomic oxygen and ultraviolet radiation, as well as thermostable polymers. [6][7][8][9][10] Organoarsenic compounds are currently being considered as ligands for transition metals because of their special properties; 11,12 however, fewer studies have been conducted with these than with their phosphorus analogs, because most organoarsenic compounds are prepared from arsenic chlorides or arsenic hydrides and require extreme caution in handling because of their volatility and toxicity. We previously reported the facile synthesis of a novel cis-1,4-diarsa-2,5-cyclohexadiene, that is, cis-1,4-dihydro-1,4-dimethyl-2,3,5,6-tetrakis(t-butoxycarbonyl)-1,4-diarsinine (cis-DHDAtBu), which was synthesized by the radical reaction of pentamethylcyclopentaarsine (cyclo-(MeAs) 5 ) and di-t-butyl acetylenedicarboxylate.…”