Rhodium-Catalysed 1,4-Additions in Water: Synthesis of Succinic Esters and β²-Amino Acid Derivatives

Abstract

The rhodium-catalysed addition of boronic acids to α-substituted activated alkenes proceeds smoothly in water resulting in a unique synthesis of both succinic esters and β²-amino acid ­derivatives.

conjugate addition - rhodium - boronic acids - succinic esters - β²-amino acids

References

For detailed reviews, see:

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3b For related work with organotin and bismuth reagents see: Huang T.-S. Li C.-J. Org. Lett.  2001,  3:  2037 

3c For recent work with potassium trifluoro(organo)borates see: Navarre L. Darse S. Genet J.-P. Eur. J. Org. Chem.  2004,  69 

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6

All compounds have been satisfactorily characterised by ¹H NMR and ¹³C NMR. ¹H NMR data (300 MHz, CDCl₃) for 3a: δ = 2.34 (1 H, dd, J = 4.8, 16.8 Hz), 2.66 (2 H, m), 3.03 (2 H, m), 3.57 (3 H, s), 3.60 (3 H, s), 7.16 (5 H, m). Compound 3c: ¹H NMR (300 MHz, CDCl₃): δ = 2.39 (1 H, dd, J = 5.7, 17.1 Hz), 2.65 (1 H, dd, J = 8.7, 17.1 Hz), 2.88 (1 H, dd, J = 10.5, 16.8 Hz), 3.09 (2 H, m), 3.57 (3 H, s), 3.60 (3 H, s), 7.42 (2 H, m), 8.01 (2 H, m). Compound 3d: ¹H NMR (300 MHz, CDCl₃): δ = 2.33 (1 H, dd, J = 5.1, 16.8 Hz), 2.61 (2 H, m), 2.98 (2 H, m), 3.57 (3 H, s), 3.60 (3 H, s), 3.72 (3 H, s), 6.76 (2 H, d, J = 8.7 Hz), 7.00 (1 H, d, J = 8.7 Hz). Compound 3e: ¹H NMR (300 MHz, CDCl₃): δ = 2.34 (1 H, dd, J = 4.5, 16.5 Hz), 2.62 (2 H, m), 3.02 (2 H, m), 3.57 (3 H, s), 3.62 (3 H, s), 3.72 (3 H, s), 6.67 (3 H, m), 7.15 (1 H, dd, J = 9.6, 17.4 Hz). Compound 3f: ¹H NMR (300 MHz, CDCl₃): δ = 2.33 (1 H, dd, J = 4.8, 17.1 Hz), 2.66 (2 H, m), 2.97 (1 H, dd, J = 6.3, 13.2 Hz), 3.14 (1 H, m), 3.55 (3 H, s), 3.59 (3 H, s), 3.75 (3 H, s), 6.79 (2 H, m), 7.00 (1 H, d, J = 9.0 Hz), 7.15 (2 H, m). Compound 3g: ¹H NMR (300 MHz, CDCl₃): δ = 2.35 (1 H, dd, J = 5.1, 16.8 Hz), 2.63 (2 H, dd, J = 8.4, 16.8 Hz), 2.78 (2 H, dd, J = 7.5, 12.9 Hz), 3.07 (2 H, m), 3.58 (3 H, s), 3.59 (3 H, s), 7.19 (2 H, d, J = 8.4 Hz), 7.83 (2 H, d, J = 8.1 Hz). Compound 3h: ¹H NMR (300 MHz, CDCl₃): δ = 2.33 (1 H, dd, J = 4.8, 16.8 Hz), 2.58 (2 H, m), 2.85 (6 H, s), 2.99 (2 H, m), 3.56 (3 H, s), 3.61 (3 H, s), 6.60 (2 H, d, J = 8.7 Hz), 6.95 (2 H, d, J = 8.7 Hz). Compound 3i: ¹H NMR (300 MHz, CDCl₃): δ = 2.32 (3 H, m), 2.64 (1 H, dd, J = 8.7, 16.5 Hz), 2.91 (1 H, m), 3.58 (3 H, s), 3.63 (3 H, s), 6.00 (1 H, m), 6.30 (1 H, d, J = 15.6 Hz), 7.19 (4 H, s).

For selected recent examples of β²-amino acid synthesis see:

7a Duursma A. Minaard AJ. Feringa BL. J. Am. Chem. Soc.  2003,  125:  3700 

7b Lee H.-S. Park J.-S. Kim BM. Gellman SH. J. Org. Chem.  2003,  68:  1575 

7c Seebach D. Schaeffer L. Gessier F. Bindschädler P. Jäger C. Josien D. Kopp S. Lelais G. Mahajan YR. Micuch P. Sebesta R. Schweizer BW. Helv. Chim. Acta  2003,  86:  1852 

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8 Basavaiah D. Krishnamacharyulu M. Rao J. Synth. Commun.  2000,  30:  2061 

9

All compounds have been satisfactorily characterised by ¹H NMR and ¹³C NMR. ¹H NMR data (300 MHz, CDCl₃) for 5a: δ = 2.85 (1 H, dd, J = 6.6, 14.1 Hz), 3.10 (1 H, dd, J = 8.7, 14.1 Hz), 3.35 (1 H, m), 3.85 (1 H, dd, J = 6.0, 13.8 Hz), 4.05 (1 H, dd, J = 8.4, 13.8 Hz), 5.00 (2 H, s), 7.10-7.25 (10 H, m), 7.67 (2 H, m), 7.78 (2 H, m). Compound 5b: ¹H NMR (300 MHz, CDCl₃): δ = 3.36 (1 H, m), 3.50 (2 H, m), 3.95 (1 H, dd, J = 4.8, 13.8 Hz), 4.15 (1 H, dd, J = 7.8, 13.8 Hz), 4.95 (2 H, s), 7.05 (2 H, dd, J = 1.7, 7.7 Hz), 7.15 (2 H, m,), 7.30 (3 H, m), 7.45 (2 H, m), 7.60-7.88 (6 H, m), 8.00 (1 H, d, J = 8.4 Hz). Compound 5c: ¹H NMR (300 MHz, CDCl₃): δ = 3.00 (1 H, dd, J = 5.9, 14.0 Hz), 3.15 (1 H, dd, J = 9.2, 14.0 Hz), 3.35 (1 H, m), 3.90 (1 H, dd, J = 6.0, 13.8 Hz), 4.08 (1 H, dd, J = 7.8, 13.8 Hz), 5.00 (2 H, s), 7.15 (2 H, m), 7.25 (3 H, m), 7.35 (1 H, m), 7.50 (1 H, d, J = 7.8 Hz), 7.70 (2 H, m), 7.85 (2 H, m), 8.00 (1 H, d, J = 8.1 Hz), 8.05 (1 H, s). Compound 5d: ¹H NMR (300 MHz, CDCl₃): δ 2.80 (1 H, dd, J = 6.6, 13.8 Hz), 3.00 (1 H, dd, J = 8.6, 14.0 Hz), 3.30 (1 H, m), 3.75 (3 H, s), 3.85 (1 H, dd, J = 6.0, 13.8 Hz), 4.05 (1 H, dd, J = 8.3, 13.7 Hz), 5.00 (2 H, s), 6.75 (2 H, d, J = 8.7 Hz), 7.05 (2 H, d, J = 8.7 Hz), 7.15 (2 H, m), 7.23 (3 H, m), 7.68 (2 H, m), 7.78 (2 H, m). Compound 5g: ¹H NMR (300 MHz, CDCl₃): δ = 2.55 (3 H, s), 2.95 (1 H, dd, J = 6.3, 14.1 Hz), 3.15 (1 H, dd, J = 8.7, 14.1 Hz), 3.35 (1 H, m), 3.90 (1 H, dd, J = 6.2, 14.0 Hz), 4.05 (1 H, dd, J = 8.1, 13.8 Hz), 5.00 (2 H, s), 7.15 (2 H, m), 7.18-7.28 (5 H, m), 7.70 (2 H, m), 7.78 (4 H, m). Compound 5j: ¹H NMR (300 MHz, CDCl₃): δ = 2.80 (1 H, dd, J = 6.5, 14.0 Hz), 3.00 (1 H, dd, J = 9.0, 14.1 Hz), 3.30 (1 H, m), 3.90 (1 H, dd, J = 6.3, 13.8 Hz), 4.05 (1 H, dd, J = 8.1, 13.8 Hz), 5.00 (2 H, s), 7.05 (2 H, d, J = 8.4 Hz), 7.15 (2 H, m), 7.23 (3 H, m), 7.29 (2 H, d, J = 8.4 Hz), 7.70 (2 H, m), 7.80 (2 H, m).

10 Calmes M. Daunis J. Mai N. Tetrahedron: Asymmetry  1997,  1641 

11 Hayashi T. Takahashi M. Takaya Y. Ogasawara M. J. Am. Chem. Soc.  2002,  124:  5052 

For examples of enantioselective additions to α,β-dehydroamino acid derivatives, see:

12a Reetz MT. Moulin D. Gosburg A. Org. Lett.  2001,  3:  4083 

12b Chapman CJ. Wadsworth KJ. Frost CG. J. Organomet. Chem.  2003,  680:  206 

12c Navarre L. Darses S. Genet J.-P. Angew. Chem. Int. Ed.  2004,  43:  719 

13 Dixon JA. Neiswender DD. J. Org. Chem.  1960,  25:  499