The Deoxygenation of Isocyanates by 2-Phenyl-3-methyl-1,3,2-oxazaphospholidine. A Convenient Method for the Preparation of Isonitriles

First examples of methylene insertion into the phosphorus(III)–nitrogen bond

“…The phosphorus is in a slightly distorted tetrahedral environment. Mukaiyama and Yokota [15] and Hudson and coworkers [7] have reported the de-oxygenation reactions of isocyanates by the cyclic phosphoramidite (2-phenyl-1,3,2-oxazaphospholidine) and acyclic phosphoramidite (diethyl-N -phenylphosphoramidite) to give the corresponding phosphine oxides and isonitrile which involves the preferential interaction of the oxygen and phosphorus atoms. Ivanov et al [16] have obtained the same product (2) via the Arbuzov reaction of RR H NCH 2 OAc (R R H Et; R H, R H Ac, Bz, Ph) with PhR HH PNEt 2 (R HH Ph, NEt 2 ) as shown in Scheme 1.…”

Total Synthesis ofN-Methylwelwitindolinone D Isonitrile

“…Rearrangement of the putative oxathiazoline then affords the isothiocyanate. Finally, desulfurization of the isothiocyanate was realized using oxazaphospholidine 23 16 to provide N -methylwelwitindolinone D isonitrile ( 5 ) in 54% yield.…”

Total Syntheses of the Elusive Welwitindolinones with Bicyclo[4.3.1] Cores

“…Although further elaboration of 25 has not yet been reported, this advanced species could possibly be used to Additionally, Trosts approach elegantly highlights the utility of the (6+3) cycloaddition methodology for building complex architectures. The route to 25 also showcases the distinctive ability of Pd catalysis, and notably p-allylpalladium chemistry, to provide intricate structural frameworks with high enantiomeric excess.…”

“…[24] Finally, desulfurization using N-methyl-P-phenyl-1,3,2-oxazaphospholidine delivered (AE)-N-methylwelwitindolinone D isonitrile (10). [25] The last steps are notable in that both C11 isothiocyanate and isonitrile moieties are accessible, as these functional groups appear in all members of the bicyclic welwitindolinones (i.e., 2-10).…”