syn-Addition of Metallated Propargylic Amines to Aldehydes. A New ­Application of Triorganozincates

Abstract

Good syn-selectivities are obtained by addition of a di-t-butyl zincate reagent derived from a propargylic amine to aldehydes.

Key words

addition reactions - aminoalcohols - organometallic reagents - zinc - stereoselectivity

References

• 1a Epsztein R. The Formation and Transformations of Allenic and α-Acetylenic Carbanions, In Comprehensive Carbanions Chemistry   Vol. B:  Buncel E. Durst T. Elsevier; Amsterdam: 1984.  p.107-175  
• 1b Yamamoto H. Propargyl and Allenyl Organometallics, In Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Fleming I. Pergamon Press; London: 1991.  p.81-98  
• 2 Ishiguro M. Ikeda N. Yamamoto H. J. Org. Chem.  1982,  47:  2225 
• 3a

  See ref. [2]

• 3b Sweifel G. Hahn G. J. Org. Chem.  1984,  49:  4567 
• 3c Normant J. Poisson J. Org Lett.  2001,  3:  1889 
• 3d Chemla F. Ferreira F. Hebbe V. Stercklen E. Eur. J. Org. Chem.  2002,  1385 
• 3e Scheidt K. Banniste T. Tasaka A. Wendt M. Savall B. Fegley G. J. Am. Chem. Soc.  2001,  124:  6981 
• 3f Marshall J. Yu R. Perkins J. J. Org. Chem.  1995,  60:  5550 
• 3g Marshall J. Adams N. J. Org. Chem.  1997,  62:  8976 
• 3h Marshall J. Grant C. J. Org. Chem.  1999,  64:  696 
• 4a Marshall J. Wang X. J. Org. Chem.  1990,  55:  6246 
• 4b Fleming I. Wareson D. J. Chem. Soc., Perkin Trans. 1  1984,  1809 
• 4c Marshall J. Maxson K. J. Org. Chem.  2000,  65:  630 
• 5 Bernaud F. Vrancken E. Mangeney P. Org. Lett.  2003,  5:  2567 
• For recent reports on conjugate addition of triorganozincates see:
• 6a Ryu M. Ikebe N. Sonoda Yamato S. Yamamura G. Komatsu M. Tetrahedron Lett.  2000,  41:  5689 
• 6b Musser CA. Richey HG. J. Org. Chem.  2000,  65:  7750 
• 7 Mori S. Hirai A. Nakamura M. Nakamura E. Tetrahedron  2000,  56:  2805 
• 9 Lautens M. Renaud JL. Sheldon H. J. Am. Chem. Soc.  2000,  122:  1804 
• 10 Linton DJ. Schooler P. Wheatley AEH. Coord. Chem. Rev.  2001,  223:  53 
• 11 A none selective attempt was performed with a Aznt-Bu₂MeLi₂ reagent prepared according: Uchiyama M. Kameda M. Mishima O. Yokoama N. Koike M. Kondo Y. Sakamoto T. J. Am. Chem. Soc.  1998,  120:  4934 
• 12 For a recent preparation of syn-β-hydroxypropargyl-oxazolidinones from optically active Ν-propargyl-oxazolidinones see: Ranslow PBD. Hegedus LS.
  de Los Rios C. J. Org. Chem.  2004,  69:  105 

8

See ref. [6b]

13

Analytical data for syn-aminoalcohols: Compound 2a: ¹H NMR (400 MHz, CDCl₃): δ = 7.32 (m, 10 H), 3.88 (d, J = 13.4 Hz, 2 H), 3.78 (br s, 1 H), 3.69 (d, J = 9.0 Hz, 1 H), 3.54 (dd, J = 4.0 Hz, J = 9.0 Hz, 1 H), 3.41 (d, J = 13.4 Hz, 2 H), 1.87 (m, 1 H), 0.65 (d, J = 6.8 Hz, 3 H), 1.02 (d, J = 6.8 Hz, 3 H), 0.26 (s, 9 H). ¹³C NMR (200 MHz, CDCl₃): δ = 138.7, 129.5, 128.8, 128.6, 100.7, 92.6, 73.5, 56.2, 55.3, 30.2, 20.8, 15.1, 0.6. Elemental analysis: C₂₄H₃₃NOSi requires C, 76.37; H, 8.28; N, 3.71%. Found: C, 76.22; H, 8.41; N, 3.69. Compound 2b: ¹H NMR (400 MHz, CDCl₃): δ = 7.33 (m, 10 H), 3.92 (br d, J = 14.0 Hz, 2 H), 3.72 (d, J = 7.0 Hz, 1 H), 3.40 (m, 3 H), 2.50 (br s, 1 H), 0.86 (s, 9 H), 0.27 (s, 9 H). ¹³C NMR (200 MHz, CDCl₃): δ = 137.9, 129.1, 128.4, 127.3, 101.7, 92.4, 75.8, 54.5, 34.5, 26.1, 0.0. Elemental analysis: C₂₅H₃₅NOSi requires C, 76.28; H, 8.96; N, 3.56%. Found: C, 76.20; H, 9.09; N, 3.54. Compound 2c: ¹H NMR (400 MHz, CDCl₃): δ = 7.30 (m, 15 H), 4.59 (d, J = 8.0 Hz, 1 H), 4.01 (d, J = 16.0 Hz, 2 H), 3.50 (d, J = 8.0 Hz, 1 H), 3.37 (d, J = 16.0 Hz, 2 H), 0.20 (s, 9 H). ¹³C NMR (200 MHz, CDCl₃): δ = 140.4, 138.0, 129.2, 127.8, 127.5, 127.1, 99.4, 92.1, 72.4, 60.8, 55.0, 0.0. Elemental analysis: C₂₇H₃₁NOSi requires C, 78.40; H, 7.55; N, 3.39%. Found: C, 78.82; H, 7.72; N, 3.63. Compound 2d: ¹H NMR (400 MHz, CDCl₃): δ = 7.39 (m, 10 H), 3.87 (d, J = 13.0 Hz, 2 H), 3.61 (td, J = 8.0 Hz, J = 4.0 Hz, 1 H), 3.41 (d, J = 13.0 Hz, 2 H), 3.2 (d, J = 8.0 Hz, 1 H), 1.75 (m, 1 H), 1.55 (m, 1 H), 1.30 (m, 6 H), 0.94 (m, 6 H), 0.20 (s, 9 H). ¹³C NMR (200 MHz, CDCl₃): δ = 138.1, 128.9, 128.3, 127.2, 100.1, 92.1, 69.3, 58.6, 55.8, 54.8, 33.6, 31.6, 25.2, 22.3, 13.8, 0.0. Elemental analysis C₂₆H₃₆NOSi requires C, 76.60; H, 9.15; N, 3.44%. Found: C, 76.54; H, 9.17; N, 3.47. Compound 2e: ¹H NMR (400 MHz, CDCl₃,): δ = 7.32 (m, 10 H), 3.92 (d, J = 13.4 Hz, 2 H), 3.79 (br s, 1 H), 3.55 (bd, 1 H), 3.45 (d, J = 13.4 Hz, 2 H), 1.80-0.87 (m, 11 H), 0.29 (s, 9 H). ¹³C NMR (200 MHz, CDCl₃): δ = 138.3, 129.1, 128.5, 127.4, 100.5, 92.3, 73.0, 55.4, 54.9, 40.0, 30.7, 26.8, 26.5, 26.3, 25.3, 0.3. Elemental analysis: C₂₇H₄₀NOSi requires C, 7.27; H, 8.89; N, 3.34%. Found: C, 77.13; H, 8.84; N, 3.49. Compound 2f: ¹H NMR (400 MHz, CDCl₃): δ = 7.31 (m, 10 H), 5.78 (dq, J = 6.6 Hz, 1 H), 5.32 (ddd, J = 7.3 Hz, J = 16.0 Hz, J = 1.6 Hz, 1 H), 4.01 (dd, J = 7.0 Hz, J = 9.7 Hz, 1 H), 3.88 (d, J = 13.4 Hz, 2 H), 3.43 (d, J = 13.4 Hz, 2 H), 3.23 (d, J = 9.0 Hz, 1 H), 1.70 (dd, J = 6.6 Hz, J = 1.2 Hz, 3 H), 0.24 (s, 9 H). ¹³C NMR (200 MHz, CDCl₃): δ = 138.2, 129.6, 129.4, 129.2, 128.6, 127.4, 99.9, 92.6, 71.1, 58.8, 55.0, 17.8, 0.2. Elemental analysis: C₂₄H₃₂NOSi requires C, 76.22; H, 8.28; N, 3.71%. Found: C, 76.26; H, 8.33; N, 3.74.