Studies Towards Total Synthesis of Antillatoxin: Indium-mediated Allylation Reaction of Carbonyl Compounds with Secondary Allylic Bromide in Aqueous Media

Abstract

We have established a new reaction condition for the indium-mediated allylation of an unreactive secondary allylic bromide with aldehydes in aqueous media to afford the corresponding homoallylic alcohols in high yields and syn diastereoselectivity. Furthermore, it has provided an easy entry to the key intermediate for the total synthesis of antillatoxin under mild and environment profitable conditions.

Key words

antillatoxin - homoallylic alcohols - indium - allylation reaction - aqueous media

References

• For pioneering work of allylic indium chemistry:
• 1a Araki S. Shimizu T. Johar PS. Jin SJ. Butsugan Y. J. Org. Chem.  1991,  56:  2538 
• 1b Araki S. Jin SJ. Idou Y. Butsugan Y. Bull. Chem. Soc. Jpn.  1992,  65:  1736 
• 1c Araki S. Katsumura N. Ito H. Butsugan Y. Tetrahedron Lett.  1989,  30:  1581 
• 1d Araki S. Shimizu T. Jin SJ. Butsugan Y. J. Chem. Soc., Chem. Commun.  1991,  824 
• 1e Johar PS. Araki S. Butsugan Y. J. Chem. Soc., Perkin Trans. 1  1992,  711 
• 1f Araki S. Butsugan Y. J. Chem. Soc., Chem. Commun.  1989,  1286 
• 1g Araki S. Imai A. Shimizu K. Yamada M. Mori A. Butsugan Y. J. Org. Chem.  1995,  60:  1841 
• 1h Araki S. Imai A. Shimizu K. Butsugan Y. Tetrahedron Lett.  1992,  33:  2581 
• For pioneering work on indium chemistry in aqueous media:
• 2a Isaac MB. Chan TH. Tetrahedron Lett.  1995,  36:  8957 
• 2b Li CJ. Chan TH. Tetrahedron Lett.  1991,  32:  7017 
• 3a Wang RB. Lim CM. Tan CH. Lim BK. Sim KY. Loh TP. Tetrahedron: Asymmetry  1995,  6:  1825 
• 3b Ho DS.-C. Sim KY. Loh TP. Synlett.  1996,  263 
• 3c Li XR. Loh TP. Tetrahedron: Asymmetry  1996,  7:  1535 
• 3d Loh TP. Ho DSC. Xu KC. Sim KY. Tetrahedron Lett.  1997,  38:  865 
• 3e Loh TP. Li XR. Tetrahedron Lett.  1997,  38:  869 
• 3f Loh TP. Cao GQ. Pei J. Tetrahedron Lett.  1998,  39:  1453 
• 4a Orjala J. Nagle GD. Hsu LV. Gervick WH. J. Am. Chem. Soc.  1995,  117:  8281 
• 4b Yokokawa F. Shioiri T. J. Org. Chem.  1998,  63:  8638 
• 4c Yokokawa F. Fujiwara H. Shioiri T. Tetrahedron Lett.  1999,  40:  1915 
• 4d Yokokawa F. Fujiwara H. Shioiri T. Tetrahedron  2000,  56:  1759 
• 4e White JD. Hanselmann R. Wardrop D. J. Am. Chem. Soc.  1999,  121:  1106 
• 5 Brown JM. Evans PL. Org. Synth.  1990,  68:  64 
• 6a Ho DS.-C. Sim KY. Loh TP. Synlett.  1996,  263 
• 6b Loh TP. Wang RB. Tan KL. Sim KY. Main Group Met. Chem.  1997,  20:  237 
• 6c Loh TP. Cao GQ. Pei J. Tetrahedron Lett.  1998,  39:  1453 
• 7 Loh TP. Cao GQ. Pei J. Tetrahedron Lett.  1998,  39:  1457