Synlett 2015; 26(03): 355-358
DOI: 10.1055/s-0034-1379735
letter
© Georg Thieme Verlag Stuttgart · New York

Proline-Catalyzed α-Aminooxylation of β-Amino Aldehydes: Access to Enantiomerically Pure syn- and anti-3-Amino-3-aryl-1,2-alkanediols

V. Venkataramasubramanian
Chemical Engineering and Process Development Division, National Chemical Laboratory, Pashan Road, Pune 411008, India   Email: a.sudalai@ncl.res.in
,
I. N. Chaithanya Kiran
Chemical Engineering and Process Development Division, National Chemical Laboratory, Pashan Road, Pune 411008, India   Email: a.sudalai@ncl.res.in
,
Arumugam Sudalai*
Chemical Engineering and Process Development Division, National Chemical Laboratory, Pashan Road, Pune 411008, India   Email: a.sudalai@ncl.res.in
› Author Affiliations
Further Information

Publication History

Received: 13 October 2014

Accepted after revision: 18 November 2014

Publication Date:
09 January 2015 (online)


Abstract

A new synthetic method for enantioselective synthesis of syn or anti-3-amino-3-aryl-1,2-alkanediols via proline catalyzed α-aminooxylation of β-amino aldehydes are described. This methodology is successfully applied to a concise and protecting group-free asymmetric synthesis of (–)-cytoxazone, (+)-epi-cytoxazone and formal synthesis of N-thiolated 2-oxazolidinone.

Supporting Information

 
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  • 17 As we have obtained the major diastereomer of >99% with enantiopurity of 93%, we believe that the stereoinduction of newly generated chiral center (C–O bond) is fully controlled by the type of proline we used, irrespective of the stereocenter in the substrate (Figure 2).
  • 18 General Experimental Procedure for the Preparation of 3-Amino-1,2-alkane Diols 1a–f To a stirred precooled (–10 °C) MeCN (25 mL) solution of β-amino aldehydes 6af (17 mmol) and nitrosobenzene (13.6 mmol) was added l-proline (0.039 g, 20 mol%). The reaction mixture was allowed to stir at the same temperature for 20 h followed by the addition of MeOH (10 mL) and NaBH4 (25 mmol) to the reaction mixture, which was stirred for further 10 min. After addition of phosphate buffer, the resulting mixture was extracted with EtOAc (3 × 30 mL), the combined organic phases were dried over anhydrous Na2SO4 and concentrated to give the crude aminooxy alcohol, which was directly taken up for the next step without purification. To a MeOH (25 mL) solution of the above crude aminooxy alcohol was added Cu(OAc)2·H2O (2.6 mmol) at 25 °C, and the reaction mixture was allowed to stir for 10 h at that temperature. After addition of phosphate buffer, the resulting mixture was extracted with CHCl3 (3 × 30 mL), and the combined organic phases were dried over anhydrous Na2SO4 and concentrated to give the crude product, which was then purified by column chromatography over silica gel using PE–EtOAc to give 3-amino-1,2-alkane diols 1af.
  • 19 (2R,3R)-3-(tert-Butoxycarbonylamino)-3-(p-tolyl)-1,2-propanediol (1c) Yield 63%; colorless solid recrystallized from CHCl3; mp 126–129 °C. [α]D 25 –57.87 (c 2.7, CHCl3); 95% ee from chiral HPLC analysis [Chiracel AD-H, n-hexane–i-PrOH (90:10), 0.5 mL min–1]: t R = 21.6 min (97%) and 27.1 min (2%). IR (CHCl3): νmax = 727, 780, 815, 884, 1049, 1101, 1163, 1247, 1287, 1365, 1391, 1506, 1683, 2929, 2976, 3366 cm–1. 1H NMR (200 MHz, CDCl3): δ = 1.42 (s, 9 H), 2.34 (s, 3 H), 2.82 (br s, 1 H), 3.31 (br s, 1 H), 3.51–3.62 (m, 2 H), 3.78 (br s, 1 H), 4.59–4.66 (m, 1 H), 5.25 (d, J = 6.7 Hz, 1 H), 7.09–7.22 (m, 4 H). 13C NMR (50 MHz, CDCl3 + DMSO-d 6): δ = 20.5, 27.9, 56.4, 62.8, 73.2, 78.4, 127.0, 128.3, 135.9, 136.4, 155.0. ESI-HRMS: m/z calcd for C15H23NO4 [M + Na]+: 304.1519, found: 304.1514. Anal. Calcd for C15H23NO4: C, 64.04; H, 8.24; N, 4.98. Found: C, 63.91; H, 8.12; N, 4.93.
  • 20 (2R,3R)-3-(tert-Butoxycarbonylamino)-3-(o-chlorophenyl)-1,2-propanediol (1d) Yield 55%; colorless gum; [α]D 25 –7.50 (c 0.32, CHCl3); 99% ee from chiral HPLC analysis [Chiracel AS-H, n-hexane–i-PrOH (95:05), 0.5 mL min–1]: t R = 25.9 min (0.5%) and 28.8 min (99.5%). IR (CHCl3): νmax = 702, 704, 1036, 1164, 1264, 1367, 1393, 1498, 1694, 2928, 3420 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.43 (s, 9 H), 2.97 (br s, 1 H), 3.39 (br s, 1 H), 3.64–3.79 (m, 2 H), 3.98–3.99 (m, 1 H), 5.15–5.17 (m, 1 H), 5.55 (br s, 1 H), 7.19–7.25 (m, 2 H), 7.27–7.42 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 28.3, 54.1, 62.8, 72.2, 80.4, 127.1, 129.0, 130.1, 133.8, 136.6, 156.3. ESI-HRMS: m/z calcd for C14H20ClNO4 [M + Na]+: 324.0973; found: 324.0970. Anal. Calcd for C14H20ClNO4: C, 55.72; H, 6.68; N, 4.64. Found: C, 55.56; H, 6.48; N, 4.47.
  • 21 (2R,3R)-3-(tert-Butoxycarbonylamino)-3-(1-naphthyl)-1,2-propanediol (1e) Yield 62%; colorless gum; [α]D 25 –13.00 (c 0.2, CHCl3); 92% ee from chiral HPLC analysis [Chiracel AD-H, n-hexane–i-PrOH (90:10), 0.5 mL min–1]: t R = 12.55 min (3.92%) and 21.64 min (96.1%). IR (CHCl3): νmax = 774, 1019, 1038, 1121, 1159, 1351, 1408, 1499, 1687, 2921, 2991, 3382 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.44 (s, 9 H), 2.66 (br s, 1 H), 3.48 (br s, 1 H), 3.76–3.86 (dd, J = 12.0, 29.3 Hz, 2 H), 4.10–4.12 (m, 1 H), 5.14 (d, J = 8.1 Hz, 1 H), 5.53–5.57 (m, 1 H), 7.48–7.57 (m, 4 H), 7.81 (d, J = 8.1 Hz, 1 H), 7.87 (d, J = 7.8 Hz, 1 H), 8.06 (d, J = 8.3 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 28.3, 51.7, 62.9, 72.9, 80.6, 122.9, 123.9, 125.3, 125.9, 126.8, 128.8, 129.1, 131.8, 134.2, 134.7, 156.8. ESI-HRMS: m/z calcd for C18H23NO4 [M + Na]+: 340.1519; found: 340.1515. Anal. Calcd for C18H23NO4: C, 68.12; H, 7.30; N, 4.41. Found: C, 67.93; H, 7.12; N, 4.31.
  • 22 (2R,3S)-3-(tert-Butoxycarbonylamino)-3-(furfuryl)-1,2-propanediol (1f) Yield 58%; colorless gum; [α]D 25 –44.32 (c 0.46, CHCl3); 90% ee. IR (CHCl3): νmax = 784, 1089, 1066, 1178, 1263, 1398, 1469, 1508, 1699, 2824, 2841, 3384, 3421 cm–1. 1H NMR (500 MHz, CDCl3): δ = 1.44 (s, 9 H), 2.95 (br s, 2 H), 3.67 (s, 2 H), 3.81 (br s, 1 H), 4.76–4.79 (m, 1 H), 5.29 (br s, 1 H), 6.32–6.34 (m, 2 H), 7.37 (br s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 28.3, 50.7, 62.8, 73.1, 80.6, 108.1, 110.5, 142.2, 151.7, 156.2. ESI-HRMS: m/z calcd for C12H19NO5 [M + Na]+: 280.1169; found: 280.1177. Anal. Calcd for C12H19NO5: C, 56.02; H, 7.44; N, 5.44. Found: C, 56.07; H, 7.36; N, 5.32.