Scandium Triflate Catalyzed Aminolysis of meso-Aziridines

Abstract

The aminolysis of meso-N-phenyl aziridines is efficiently catalyzed with just 1 mol% of Sc(OTf)₃ and furnishes valuable 1,2-diamines in good to excellent yields.

Key words

amine - aziridine - catalysis - 1,2-diamine - scandium

References and Notes

• Reviews:
• 1a Schneider C. Synthesis  2006,  3919 
• 1b Pastor IM. Yus M. Curr. Org. Chem.  2005,  9:  1 
• 1c Jacobsen EN. Wu MH. Comprehensive Asymmetric Catalysis   Vol. 2:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999.  p.649 
• Reviews:
• 2a Aziridines and Epoxides in Organic Synthesis   Yudin AK. Wiley-VCH; Weinheim: 2006. 
• 2b Pineschi M. Eur. J. Org. Chem.  2006,  4979 
• 2c Hu XE. Tetrahedron  2004,  60:  2701 
• 2d McCoull W. Davis FA. Synthesis  2000,  1347 
• For select catalytic processes, see:
• 3a Wu J. Sun X. Li Y. Eur. J. Org. Chem.  2005,  4271 
• 3b Bisai A. Bhanu Prasad BA. Singh VK. Tetrahedron Lett.  2005,  46:  7935 
• 3c Watson IDG. Yudin AK. J. Org. Chem.  2003,  68:  5160 
• 3d Swamy NR. Venkateswarlu Y. Synth. Commun.  2003,  33:  547 
• 3e Yadav JS. Reddy BVS. Rao KV. Raj KS. Prasad AR. Synthesis  2002,  1061 
• 3f Cossy J. Bellosta V. Alauze V. Desmurs JR. Synthesis  2002,  2211 
• 3g Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
• 3h Chandrasekhar M. Sekar G. Singh VK. Tetrahedron Lett.  2000,  41:  10079 
• 3i Sekar G. Singh VK. J. Org. Chem.  1999,  64:  2537 
• 3j Meguro M. Asao N. Yamamoto Y. Tetrahedron Lett.  1994,  35:  7395 
• For select catalytic processes, see:
• 4a Bhanu Prasad BA. Sanghi R. Singh VK. Tetrahedron  2002,  58:  7355 
• 4b Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
• 4c Bhanu Prasad BA. Sekar G. Singh VK. Tetrahedron Lett.  2000,  41:  4677 
• For select catalytic processes, see:
• 5a Yadav JS. Reddy BVS. Baishya G. Venkatram Reddy P. Narsaiah AV. Catal. Commun.  2006,  7:  807 
• 5b Wu J. Sun X. Li Y. Eur. J. Org. Chem.  2005,  4271 
• 5c Yadav JS. Subba Reddy BV. Baishya G. Reddy PV. Harshavardhan SJ. Synthesis  2004,  1854 
• 5d Hou X.-L. Fan R.-H. Dai L.-X. J. Org. Chem.  2002,  67:  5295 
• 5e Wu J. Hou X.-L. Dai L.-X. J. Chem. Soc., Perkin Trans. 1  2001,  1314 
• 5f Hayashi M. Ono K. Hoshimi H. Oguni N. J. Chem. Soc., Chem. Commun.  1994,  2699 
• 5g For the first catalytic, enantioselective process, see: Luo Z.-B. Hou X.-L. Dai L.-X. Tetrahedron: Asymmetry  2007,  18:  443 
• 6a Mita T. Fujimori I. Wada R. Wen J. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2005,  127:  11252 
• 6b Fukuta Y. Mita T. Fukuda N. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  6312 
• 6c For previous catalytic, enantioselective azide addition to meso-aziridines, see: Li Z. Fernandez M. Jacobsen EN. Org. Lett.  1999,  1:  1611 
• 7a Schneider C. Sreekanth AR. Mai E. Angew. Chem. Int. Ed.  2004,  43:  5691 ; Angew. Chem. 2004, 116, 5809
• 7b Mai E. Schneider C. Chem. Eur. J.  2007,  13:  2729 
• 7c Tschöp A. Marx A. Sreekanth AR. Schneider C. Eur. J. Org. Chem.  2007,  2318 
• 7d Nandakumar MV. Tschöp A. Krautscheid H. Schneider C. Chem. Commun.  2007,  2756 
• 7e Mai E. Schneider C. Synlett  2007,  2136 
• 8 Scandium triflate has been shown to catalyze the addition of acid anhydrides to aziridines, see: Yadav JS. Reddy BVS. Sadashiv K. Harikishan K. Narsaiah AV. J. Mol. Catal. A: Chem.  2004,  220:  153 
• 9 Ferraris D. Drury WJ. Cox C. Lectka T. J. Org. Chem.  1998,  63:  4568 

10

General Procedure for Ring Opening of meso -Aziridines
To a solution of Sc(OTf)₃ (5 mg, 0.01 mmol) in CH₂Cl₂ (5 mL), were added N-phenyl aziridine (1.00 mmol) and amine (1.50 mmol), and the mixture was stirred at r.t. for 1 h (monitored by TLC). The solvent was removed in vacuo and the crude product was purified through flash chromatog-raphy using pentane-EtOAc (15:1) as eluent. For analytical and spectroscopic details of the products see ref. 3.