Ni-Catalyzed C–P Coupling of Aryl, Benzyl, or Allyl Ammonium Salts with P(O)H Compounds

Abstract

A methodology that allows for the construction of C–P bonds via the nickel-catalyzed cross-coupling of organoammonium salts with appropriate phosphorus nucleophiles has been developed. Aryl-, pyridyl-, benzyl-, and allyl-ammonium triflates can be employed as the electrophiles. The employed phosphorus-based nucleophiles included diaryl/dibutyl phosphine oxide, dialkyl phosphonates, and ethyl phenylphosphinate. Functional groups OMe, CN, CF3, F, Cl, C­(O)­NMe2, and C­(O)tBu were tolerated.

A Concise Synthesis ofrac‐Ambrox®viathe Palladium(0)‐Catalyzed Carboalkoxylation of an Allylic Ammonium Salt, as Compared to a Formaldehyde HeteroDiels–AlderApproach

“…For Ni-catalyzed CÀ P coupling of benzyl and allyl ammonium salts with R 2 P(O) H derivatives, see ref. [85]. 23 conversion are increased in this later case.…”

Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds

“…(Naphthalen-1-ylmethyl)diphenylphosphine oxide (3N) [23] The reaction was conducted by using 2.0 equiv of HCOONa. Purification by PTLC ((6-Methoxynaphthalen-2-yl)methyl)diphenylphosphine oxide (3O) [24] Purification by PTLC (hexane/acetone = 1:1) afforded 3O as a white solid (38.5 mg, 52% yield). 1 [22] The reaction was conducted by using 2.0 equiv of HCOONa.…”

“…Purification by PTLC (hexane/acetone = 1:3) afforded 3V as a white solid (39.2 mg, 52% yield). 1 [24]…”

Pd-Catalyzed C4-Dearomative Allylation of Benzyl Ammoniums with Allylstannanes

“…[4] Moreover, a meta-C-H borylation of benzyl ammoniums by using an electrostatic interaction between the ammonium moiety and a specially designed iridium catalyst was reported by the Phipps group. [5] Although these examples used aminomethyl groups as well as ammoniums as the directing group, ammoniums are also known to function as the leaving group. Namely, benzylammoniums can participate in benzyl coupling reactions catalyzed by nickel and palladium complexes.…”

“…give 7 in good yield. As another example, we succeeded in 23 the C3-borylation of ammonium 8 under Phipps' C-H 24 borylation conditions [5] followed by the dearomative 25 allylation of 9 to give boron-bearing compound 10. Because 26 of the instability of 10, we directly treated the crude 10 with 27…”