Addition of Functionalized Nucleophiles to a Bridgehead Bromoketone

Abstract

The reaction of bromoketone 1 with a variety of functionalized organolithiums is presented. In most cases, carbonyl addition followed by quasi-Favorskii rearrangement takes place to afford the rearrangement product in good yield. The utility of products from such a reaction is demonstrated in the synthesis of 22 from 14 via allylation and ring-opening/ring-closing metathesis.

Key words

cycloaddition - quasi-Favorskii rearrangement - lithium - metathesis

References

• 1a Harmata M. Bohnert G. Org. Lett.  2001,  5:  59 
• 1b Harmata M. Rashatassakhon P. Org. Lett.  2001,  3:  2533 
• 1c Harmata M. Rashatassakhon P. Tetrahedron Lett.  2001,  42:  5593 
• 1d Harmata M. Shao L. Abeywardane A. Tetrahedron Lett.  1999,  40:  1075 
• 1e Harmata M. Shao L. Synthesis  1999,  1543 
• 2 Harmata M. Wacharasindhu S. J. Chem. Soc., Chem. Commun.  2003,  2942 
• 3 Harmata M. Wacharasindhu S. J. Org. Chem.  2005,  70:  725