Asymmetric Synthesis of Aziridine 2-Phosphonates from Enantiopure Sulfinimines (N-Sulfinyl Imines). Synthesis of α-Amino Phosphonates
- 22 February 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (6) , 2410-2419
- https://doi.org/10.1021/jo020707z
Abstract
An aza-Darzens reaction, involving the addition of chloromethylphosphonate anions to enantiopure sulfinimines, has been developed for the asymmetric synthesis of aziridine 2-phosphonates. Best results involve cyclization of the syn and anti diastereomerically pure α-chloro-β-amino phosphonates to cis- and trans-N-sulfinyl aziridine 2-phosphonates, respectively, with n-BuLi. A transition-state hypothesis is proposed wherein the chloromethylphosphonate anion adds to the C−N bond on the side that is opposite the bulky p-tolyl sulfinyl group. The N-sulfinyl group is easily removed by treatment with MeMgBr or TFA/MeOH, which affords the NH-aziridines in good yield. Using transfer hydrogenation conditions, the NH-aziridines were regioselectively opened to the corresponding enantiopure α-amino phosphonates without N-activation and in excellent yield.Keywords
This publication has 28 references indexed in Scilit:
- An efficient synthesis of α- and β-aminophosphonic esters from α-amino acidsTetrahedron Letters, 2002
- Aziridination of α,β-unsaturated phosphonic estersTetrahedron Letters, 2001
- The Catalytic Asymmetric Aminohydroxylation of Unsaturated PhosphonatesThe Journal of Organic Chemistry, 1999
- Synthesis of α-aminoalkylphosphonates from vinylphosphonates via aziridinylphosphonatesTetrahedron, 1997
- Aziridines and Azirines: Fused-ring DerivativesPublished by Elsevier ,1996
- Aziridines and Azirines: MonocyclicPublished by Elsevier ,1996
- Chiral Aziridines—Their Synthesis and Use in Stereoselective TransformationsAngewandte Chemie International Edition in English, 1994
- A Novel Asymmetric Synthesis of α- and β-Amino Aryl Phosphonic AcidsSynlett, 1993
- Highly Functionalized Aziridines II; A Facile Synthesis of Diethyl Aziridinylphosphonates and 2-ChloroaziridinylphosphonatesHETEROCYCLES, 1989
- Aziridine-2-phosphonic acid, the valuable synthon for synthesis of 1-amino-2-functionalized ethanephosphonic acidsTetrahedron, 1985