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Synlett 2006(12): 1871-1874  
DOI: 10.1055/s-2006-948195
LETTER
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Alkynyl Additions to Aldehydes Catalyzed by Tunable ­Oxovanadium(V) Complexes of Schiff Bases of β-Amino Alcohols

Sheng-Hsiang Hsieh, Han-Mou Gau*
Department of Chemistry, National Chung-Hsing University, Taichung 402, Taiwan
Fax: +886(4)22862547; e-Mail: hmgau@dragon.nchu.edu.tw;
Further Information

Publication History

Received 16 March 2006
Publication Date:
24 July 2006 (online)

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Abstract

The first example of asymmetric alkynyl additions to ­aldehydes catalyzed by oxovanadium(V) catalysts of tridentate Schiff bases of β-amino alcohols 3a-h is reported. Catalytic reactions employing the best-performing catalyst 3g furnish chiral ­propargyl alcohols in good to excellent enantioselectivities from 73% to 99% ee.

Key words

oxovanadium complex - alkynylation - Schiff bases - β-amino alcohols - aromatic aldehydes - aliphatic aldehydes - propargyl alcohols

14

General Procedures for Synthesis of Oxovanadium(V) Complexes 3a-h.
To a solution of a Schiff base (1.00 mmol) in 10 mL appropriate alcohol, VO(Oi-Pr)3 (0.24 mL, 1.0 mmol) was added at r.t. The mixture was stirred for 1 h and the solvent was removed under reduced pressure to give a quantitative yield of the product. All compounds were characterized by 1H NMR and 13C NMR spectroscopy and by elemental analyses. Two sets of NMR resonances are observed for each complex due to the presence of two isomers in solution. Spectroscopic data of complexes 3c and 3g as examples are listed in the following. The two isomers are designated as major and minor based on relative intensities of resonances. 1H NMR spectra for the two isomers in the phenyl region are overlapped and resonances of the minor are included in data of the major.
Complex 3c: dark green solid. 1H NMR (400 MHz, CDCl3): δ (major, 69%) = 7.56 (s, 1 H, CH=N), 7.50-6.76 (m, Ph), 6.43 (d, J = 3.2 Hz, 1 H, CHO), 5.34-5.26 (m, 2 H, OCH 2 ), 4.20 (d, J = 6.0 Hz, 1 H, CHN), 3.61 (dd, J = 7.6, 9.2 Hz, 1 H, CH A H B Ph), 2.62 (dd, J = 2.0, 9.0 Hz, 1 H, CH A H B Ph), 1.59 (t, J = 5.2 Hz, 3 H, CH 3 ) ppm; δ (minor, 31%) = 7.57 (s, 1 H, CH=N), 6.65 (d, J = 3.6 Hz, 1 H, CHO), 5.40-5.36 (m, 2 H, OCH 2 ), 4.53 (d, J = 7.2 Hz, 1 H, CHN), 2.57 (dd, J = 2.4, 9.2 Hz, 1 H, CH A H B Ph), 2.47 (dd, J = 7.6, 9.2 Hz, 1 H, CH A H B Ph), 1.69 (t, J = 4.8 Hz, 3 H, CH 3 ) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 163.26, 162.86, 162.71, 140.50, 137.86, 137.11, 135.82, 135.57, 132.45, 132.35, 130.19, 130.14, 128.70, 128.60, 128.55, 128.47, 127.62, 127.43, 127.01, 126.77, 126.67, 126.05, 125.95, 124.98, 119.78, 119.51, 118.84, 93.35, 90.92, 87.19, 86.39, 84.50, 79.54, 79.07, 78.62, 42.02, 36.23, 36.11, 25.58, 19.13, 17.97, 17.74. Anal. Calcd for C24H24NO4V (%): C, 65.31; H, 5.48; N, 3.17. Found: C, 65.66; H, 5.08; N, 3.57.
Complex 3g: brown solid. 1H NMR (400 MHz, CDCl3): δ (major, 71%) = 7.45-6.77 (m, CH=N, Ph), 4.89 (d, J = 4.0 Hz, 1 H, CHN), 4.85 (ddd, J = 6.8, 11.4, 28.0 Hz, 2 H, OCH 2), 4.05 (d, J = 12.0 Hz, 1 H, CHO), 3.83 (dd, J = 12.4, 12.4 Hz, 1 H, CH A H B Ph), 3.43 (d, J = 13.2 Hz, 1 H, CH A H B Ph), 2.16-2.06 (m, 1 H, CH2 CH), 1.18 (s, 9 H, t-Bu), 1.03 [d, J = 6.8 Hz, 6H, CH(CH 3 )2] ppm; δ (minor, 29%) = 5.24 (d, J = 4.0 Hz, 1 H, CHN), 5.05 (ddd, J = 6.8, 11.0, 30.8 Hz, 2 H, OCH 2), 4.32 (d, J = 11.6 Hz, 1 H, CHO), 3.28 (d, J = 14.0 Hz, 1 H, CH A H B Ph), 2.62 (dd, J = 12.4, 12.4 Hz, 1 H, CH A H B Ph), 2.40-2.22 (m, 1 H, CH2CH), 1.21 (s, 9 H, t-Bu), 1.12 [d, J = 6.8 Hz, 6 H, CH(CH 3 )2] ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 165.18, 163.73, 161.93, 161.78, 137.98, 137.17, 135.37, 135.08, 132.25, 132.15, 130.20, 130.03, 128.44, 128.38, 126.67, 126.60, 120.01, 119.34, 119.04, 118.97, 118.64, 118.57, 98.05, 94.60, 89.84, 88.71, 83.31, 78.13, 36.77, 36.31, 35.81, 31.91, 31.60, 27.55, 27.12, 19.47, 19.41, 18.79. Anal. Calcd for C24H32NO4V (%): C, 64.13; H, 7.18; N, 3.12. Found: C, 63.72; H, 7.42; N, 3.59.