title: Phosphonate–phosphinate rearrangement.
abstract: LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH3O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH3O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate.
authors.forename: Renzhe
authors.initials: R
authors.lastname: Qian
authors.forename: Alexander
authors.initials: A
authors.lastname: Roller
authors.forename: Friedrich
authors.initials: F
authors.lastname: Hammerschmidt
mesh_terms: D000577:Amides / Q000737:chemistry*; D001669:Biochemical Phenomena; D018020:Lithium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D063065:Organophosphonates / Q000138:chemical synthesis* / Q000737:chemistry; D010627:Phenethylamines / Q000737:chemistry*; D010756:Phosphoric Acids / Q000737:chemistry*; D013764:Tetrahydronaphthalenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: C000600033:1,2,3,4-tetrahydronaphthalen-1-ylamine; D000577:Amides; D018020:Lithium Compounds; D063065:Organophosphonates; D010627:Phenethylamines; D010756:Phosphoric Acids; D013764:Tetrahydronaphthalenes; C011067:phosphoramidic acid