The samarium grignard reaction. In situ formation and reactions of primary and secondary alkylsamarium(III) reagents

Article abstract of DOI:10.1021/ja00041a024

This work shows that primary and secondary radicals are rapidly reduced in THF/HMPA to form primary- and secondary-alkylsamarium reagents. The primary- and secondary-radicals can be formed either by direct SmI₂ reduction of primary- and secondary-halides or by a previous rapid radical cyclization. The samarium reagents have moderate stability in solution, and they react with a variety of typical electrophiles, including aldehydes and ketones. The work further shows that organosamarium intermediates can be involved in the traditional samarium Barbier reaction of aldehydes and ketones conducted in THF/HMPA. A new procedure called the "samarium Grignard" method is introduced, and it is suggested that this new procedure will have considerably more scope and generality than the samarium Barbier reaction.