Homogeneous, palladium-catalyzed, selective hydrogenolysis of organohalides

Synthesis and Crystal Structure of Bis(2,3-dihydro-3-methylbenzothiazole-2-ylidene)palladium(II) Diiodide: The First Palladium Complex with Benzothiazole Carbene Ligands Suitable for Homogeneous Catalysis

“…Another advantage of this catalyst lies in the absence of competing Pd-catalysed hydrogenolysis of haloarenes by formate. [18,19] In conclusion, the activity of the catalyst described here compares favourably with those of other Pd-carbene complexes. The present complex has a series of advantages over other catalysts and thus has much potential for future applications.…”

Ionic and Organometallic‐Catalyzed Organosilane Reductions

“…Aryl bromides and iodides, but not chlorides, are reduced with PMHS/Pd(PPh 3 ) 4 in moderate to excellent yields. 199 This system also reduces vinyl bromides. 199 p-Chlorobenzophenone is reduced to benzophenone with sym-tetramethyldisiloxane and Ni/C in excellent yield (Eq.…”

“…Bromopropiophenone is reduced to propionic acid with polymethylhydrosiloxane (PMHS, 38), an inexpensive industrial commodity, and Pd(PPh 3 ) 4 in 35% yield 199. This reagent combination also reduces α-halo ketones in high yields (Eq.…”

Tetrakis(triphenylphosphine)palladium(0)

“…At elevated temperatures (100-110 • C), ArBr and ArI are reduced to ArH in the presence of catalytic Pd(Ph 3 P) 4 and reducing agents such as HCO 2 Na (eq 35), 3,87 NaOMe, 88 and PMHS/Bu 3 N. 3 Aldehydes, ketones, esters, acids, and nitro substituents are unaffected. ArCl are poor substrates unless the aromatic nucleus is substituted with NO 2 .…”

“…112 Rearrangements, Isomerizations and Eliminations. Pd(Ph 3 P) 4 catalyzes several [3,3]-sigmatropic rearrangements including those of O-allyl phosphoro-and phosphonothionates to the corresponding S-allyl thiolates (eq 41) 113 and allylic N-phenylformimidates to N-allyl-N-phenylformamides (eq 42). 114 The 3-aza-Cope rearrangement of N-allylenamines to γ,δ-unsaturated imines (eq 43) 115 and a Claisen rearrangement but with no allyl inversion 116 have also been described.…”