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DOI: 10.1055/s-2004-822924
Allylation of Carbonyl Compounds Mediated by Nanometer-Sized Bismuth in Water
Publication History
Publication Date:
28 April 2004 (online)
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Abstract
It is found that nanometer-sized bismuth mediates the allylation of carbonyl compounds in water to afford the corresponding homoallylic alcohol in high yields. Nanometer-sized bismuth is much more effective than regular bismuth powder in this reaction.
Key words
allylation - carbonyl compounds - water - aromatic - stereoselectivity
- 1
Bell AT. Science 2003, 299: 1689 ; and references therein -
2a
Zhang W.Liao S.Xu Y.Zhang Y. Synth. Commun. 1997, 27: 3977 -
2b
Wang ZY.Zha ZG.Zhou CL. Org. Lett. 2002, 4: 1683 - For reviews:
-
3a
Li CJ. Chem. Rev. 1993, 93: 2023 -
3b
Li CJ. Tetrahedron 1996, 52: 5643 -
3c
Lubineau A.Auge J.Queneau Y. Synthesis 1994, 741 -
3d
Li CJ. Acc. Chem. Res. 2002, 35: 533 -
4a
Yanagisawa A.Nakashima H.Ishita A.Yamamoto H. J. Am. Chem. Soc. 1996, 118: 4723 -
4b
Loh TP.Xu J.Loh T. Tetrahedron Lett. 1999, 40: 2431 -
4c
Li CJ.Meng Y.Yi XH. J. Org. Chem. 1998, 63: 7498 -
4d
Tan XH.Shen B.Liu L.Guo QX. Tetrahedron Lett. 2002, 43: 9373 -
4e
Wang ZY.Yuan SZ.Li CJ. Tetrahedron Lett. 2002, 20: 5097 -
4f
Podlech J.Maier TC. Synthesis 2003, 633 -
4g
Loh TP.Lin MJ.Tan KL. Tetrahedron Lett. 2003, 44: 507 - 5
Li YD.Wang JW.Deng ZX.Wu YY.Sun XM.Yu DP.Yang PD. J. Am. Chem. Soc. 2001, 123: 9904 - For the allylation reaction of carbonyl compounds mediated by regular Bi in aqueous media under different conditions:
-
7a
Miyamoto H.Daikawa N.Tanaka K. Tetrahedron Lett. 2003, 44: 6963 -
7b
Andrews PC.Peatt AC.Raston CL. Green Chem. 2001, 3: 313 -
7c
Laskar DD.Gohain M.Prajapati D.Sandhu JS. New J. Chem. 2002, 26: 193 -
7d
Miyoshi N.Nishio M.Murakami S.Fukuma T.Wada M. Bull. Chem. Soc. Jpn. 2000, 689 - 9
Zha ZG.Xie Z.Zhou CL.Wang ZY.Wang YS. Chin. J. Chem. 2002, 20: 1477 - 11
Zha ZG.Wang YS.Yang G.Zhang L.Wang ZY. Green Chem. 2002, 4: 578 - 13
Chan TH.Yang Y.Li CJ. J. Org. Chem. 1999, 64: 4452 -
14a
Anastas PT.Warner JC. Green Chemistry: Theory and Practice Oxford University Press; New York: 1997. -
14b
Li CJ.Chan TH. Organic Reactions in Aqueous Media John Wiley & Sons; New York: 1997. -
14c
Bieler LW.Storch EC.Malvestiti I.Silva MF. Tetrahedron Lett. 1998, 39: 9393
References
General procedure for the allylation of aldehydes with allyl bromide mediated by Bi nanotubes in distilled water. To a suspension of bismuth nanotube (0.250 g, 1.2 mmol) and allyl bromide (0.18 mL, 2 mmol) in water was added benzaldehyde (0.11 mL, 1 mmol). The reaction mixture was stirred at r.t. and monitored by TLC. After 2-7 h, the mixture was filtered to remove the white precipitate and the filtrate was extracted with ether (3 × 15 mL). The combined organic layer was washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue, in most cases, afforded the corresponding homoallylic alcohols in sufficient purity as judged by TLC and 1H NMR. When necessary, purification was performed by flash column chromatography over silica gel.
8General procedure for the allylation of aldehydes with allyl bromide mediated by regular Bi in distilled water. To a suspension of bismuth powder (0.250 g, 1.2 mmol) and allyl bromide (0.18 mL, 2 mmol) in water was added benzaldehyde (0.11 mL, 1 mmol). The reaction mixture was stirred at r.t. and monitored by TLC. After 24 h, the mixture was filtered to remove the white precipitate and the filtrate was extracted with ether (3 × 15 mL). The combined organic layer was washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography over silica gel, affording the corresponding homoallylic alcohols.
10General procedure for the allylation of aldehydes with allyl bromide mediated by in situ nano-Bi. To a suspen-sion of Bi(NO3)3 (0.728 g, 1.5 mmol) in water (4 mL) was added CTAB (0.1 mmol) and a solution of KBH4 (0.106 g, 2 mmol) in H2O (2 mL). After the addition was completed, the reaction mixture was stirred continuously for 15 min, then benzaldehyde (0.11 mL, 1 mmol) and allyl bromide (0.18 mL, 2 mmol) were added. Then the reaction mixture was treated as described in ref. 10.
12See Figure [2] :
Figure 2