Completely stereoselective PC bond formation via base-induced [1,3]- and [1,2]-intramolecular rearrangements of aryl phosphinates, phosphinoamidates and related compounds: generation of P-chiral β-hydroxy, β-mercapto- and α-amino tertiary phosphine oxides and phosphine sulfides

N → C2 → C3 migration of the dichlorophosphino group in the synthesis of phosphorylated NH‐pyrroles

“…As shown previously, the C 2 → C 3 migration of the dibromophosphino group in the Nmethylpyrrole ring is catalyzed by pyridine hydrobromide [11]. We have also observed the effect of acidic impurities on the N → C 2 → C 3 migration of the dichlorophosphino group.…”

“…c 2008 Wiley Periodicals, Inc. [3][4][5][6][7], as well as the reactions of 2,4-dimethylpyrroles and 2,3,5-trimethylpyrroles with chlorophosphites that occur nonselectively at the pyrrole NH group and the C 2 and C 3 atoms [8]. Several N → C 2 and C 2 → C 3 migrations of electrophilic groups (C O, SO 2 , P O, and PBr 2 ) in pyrroles are also known [9][10][11][12].…”

A novel bifunctional Ti(IV) complex catalyzed asymmetric silylcyanation of aldehydes

“…( R )‐BINOL in THF was treated with NaH (2.2 equiv) followed by the dropwise addition of diphenylphosphinic chloride (2.2 equiv), to give the corresponding phosphinate ( R )‐1 quantitatively without further purification 39. The rearrangement of ( R )‐1 upon treatment with lithium diisopropylamide (10 equiv) in THF at –78°C gave L1 as a colorless crystal after being purified by column chromatography (200–300 mesh, gradient eluted with dichloromethane/ethyl acetate) 40.…”

“…(R)‐3,3′‐Bis(diphenylphosphinoyl)‐BINOL ( L1 ) was purified by column chromatography (200–300 mesh, gradient eluted with dichloromethane/ethyl acetate) 40. Yield: 51%.…”

α,β-Aziridinylphosphonates by lithium amide-induced phosphonyl migration from nitrogen to carbon in terminal aziridines

“…More recently, Modro et al reported a similar ortho -lithiation followed by [1,3]-shift of a phosphonyl group ( 6 → 7 , Scheme 2) [18]; related processes have been observed with diazaphospholidine oxides [19] and bicyclic phosphoric triamides [20]. Benzylic lithiation-induced N - to C -[1,2]-anionic phosphonyl rearrangements ( 8 → 9 , Scheme 2) were developed by Hammerschmidt and Hanbauer [21], and a stereoretentive N - to C -[1,2]-shift in an α-lithiated pyrrole involving a chiral tert -butyl(phenyl)phosphinyl group has been reported [22]. …”