Highly Efficient Allylation of Aldehydes and Three-Component Synthesis of Homoallylamines Using Bismuth Triflate Catalyst

Abstract

Bismuth triflate catalyzed allylation of a variety of aldehydes and aldimines using allyltributylstannane has been presented. The reaction proceeds rapidly and yields corresponding homoallylic alcohols and homoallylic amines in good yields. The bismuth triflate displays manifold activity over the La, Yb, and Sc triflates. The catalyst is reused for allylation of aldehydes and aldimines without significant loss of catalytic activity for four cycles.

allylation - aldehydes and aldimines - bismuth triflate - Bronsted acids - turnover frequency

References

1a Pereyre M. Quintard J.-P. Rahm A. Tin in Organic Synthesis   Butterworths; London: 1987.  p.216 

1b Nishigaichi Y. Takuwa A. Naruta Y. Maruyama K. Tetrahedron  1993,  49:  7395 

1c Yamamoto Y. Asao N. Chem. Rev.  1993,  93:  2207 

2 Keck GE. Enholm J. J. Org. Chem.  1985,  50:  146 

3a Akkiyama T. Iwai J. Synlett  1998,  273 

3b Kobayashi S. Busujima T. Nagayama S. Chem. Commun.  1998,  19 

4a Yanagisawa A. Morodome M. Hiroshi Nakashimma H. Yamamoto Y. Synlett  1997,  1309 

4b Loh T. Xu J. Tetrahedron Lett.  1999,  40:  2431 

5 Kobayashi S. Busujima T. Nagayama S. Chem. Commun.  1998,  19 

6a Suzuki H. Ikegami T. Matano Y. Synthesis  1997,  249 

6b Marshall JA. Chemtracts  1997,  10:  1064 

6c Vidal S. Synlett  2001,  1194 

7a Desmurs JR. Labrouillere M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Tetrahedron Lett.  1997,  38:  8871 

7b Repichet S. Leroux C. Dubac J. Eur. J. Org. Chem.  1998,  2743 

8a Repichet S. Leroux C. Hernandez P. Dubac J. Desmurs JR. J. Org. Chem.  1999,  64:  6479 

8b Repichet S. Le Roux C. Dubac J. Tetrahedron Lett.  1999,  40:  9233 

9a Laurent-Robert H. Le Roux C. Dubac J. Synlett  1998,  1138 

9b Garrigues B. Gonzaga F. Robert H. Dubac J. J. Org. Chem.  1997,  62:  4880 

9c Robert H. Garrigues B. Dubac J. Tetrahedron Lett.  1998,  39:  1161 

10a Yanagisawa A. Morodome M. Nakashima H. Yamamoto H. Synlett  1997,  1309 

10b Loh T.-P. Xu J. Tetrahedron Lett.  1999,  40:  2431 

11 Orita A. Tanahashi C. Kakuda A. Otera J. Angew. Chem. Int. Ed.  2000,  39:  2877 

12 Repichet S. Zwick A. Vendier L. Le Roux C. Dubac J. Tetrahedron Lett.  2002,  43:  993 

13a Aspinall HC. Greeves N. Mclver EG. Tetrahedron Lett.  1998,  39:  9283 

13b Aspinall HC. Bissett JS. Greeves N. Levin D. Tetrahedron Lett.  2002,  43:  319 

14

Typical Experimental Procedure for the Allylation of Aldehydes: To a stirred solution of p-chlorobenzaldehyde (1 mmol), benzoic acid (1 mmol) and allyltributylstannane (1.2 mmol) in acetonitrile (5 mL) at r.t. was added bismuth triflate (2 mol%). The mixture was stirred at r.t. until reaction was completed as indicated by TLC. The catalyst, which was precipitated at the end of the reaction, was filtered off. The filtrate was concentrated under vacuum to obtain a crude product and was purified by column chromatography (10% ethyl acetate-hexane) (164 mg, 90%). ¹H NMR (200 MHz, CDCl₃) δ 2.01(d, 1 H, OH), 2.52 (m, 2 H, CH₂), 4.75 (t, 1 H,CH), 5.14-5.20 (m, 2 H, 2 vinyls), 5.82 (m, 1 H, vinyl), 7.20-7.30 (m, 4 H, aromatic) [Lit [10a] ].

15

Typical Experimental Procedure for the One-Pot Allylation of Aldimines: To a stirred solution of p-chlorobenzaldehyde (1 mmol), benzoic acid (1 mmol), allyltributylstannane (1.2 mmol) and o-chloroaniline (1 mmol) in acetonitrile (5 mL) at r.t. was added bismuth triflate (2 mol%). The mixture was stirred at r.t. until reaction was completed as indicated by TLC. The catalyst, which was precipitated at the end of the reaction, was filtered off. The filtrate was concentrated under vacuum to obtain a crude product and was purified by column chromatography (10% ethyl acetate-hexane) (189 mg, 65%). ¹H NMR (200 MHz, CDCl₃) δ 2.52 (m, 2 H, CH₂), 4.40 (t, 1 H, CH), 5.14-5.20 (m, 2 H, 2 vinyls), 5.80 (m, 1 H, vinyl), 6.20 (d, 1 H, aromatic), 6.6 (m, 2 H, aromatic), 6.80-7.00 (m, 1 H, aromatic), 7.20-7.30 (m, 4 H, aromatic) [Lit [16] ].

16 Wang D.-K. Zhou Y.-G. Tang Y. Hou X.-L. Dai L.-X. J. Org. Chem.  1999,  64:  4233