78 [1-(アリールイミノ)アルキル]サマリウム(III)の生成と天然物合成への応用(ポスター発表の部)

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Nucleophilic introduction of acyl groups into organic molecules has been often achieved by use of synthetic equivalents of acyl anions. Although acylmetals may be potentially useful for this purpose, synthetic application of acylmetals has been so far limited. We have been studying the generation and utilization of N-substituted [1-(N-substituted imino)alkyl]metal compounds, nitrogen analogue of acylmetals, which are also expected to act as acyl anion equivalents. We now report a facile preparation of an acyl anion equivalent, i.e., [1-(arylimino)alkyl]samarium(III), by the samarium(II) iodide mediated coupling reaction of alkyl halide with aryl isocyanide and its reaction with carbonyl compounds. Alkyl halide was treated with 2,6-xylyl isocyanide (1) and samarium(II) iodide to generate [1-(arylimino)alkyl]samarium(III) (3). This intermediate samarium(III) species reacted with carbonyl compounds to afford α-hydroxy imines (4), which were readily transformed to the corresponding α-hydroxy ketones (5) by acidic hydrolysis. A useful synthetic equivalent to the α-hydroxyacetyl anion was developed by use of benzyl chloromethyl ether (6) as alkyl halide in the reaction mentioned above. D-Ribulose (12) was successfully synthesized by the reaction of [1-(arylimino)alkyl]samarium(III) (7), prepared from benzyl chloromethyl ether (6), with protected glyceraldehyde.
天然有機化合物討論会の論文
1990-09-25