31 l-Abietic Acidよりd-Kaurene,d-Phyllocladene,l-Hibaeneの合成 : 13位Isopropyl基の変換

概要

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d-Kaurene (17) and d-phyllocladene (18) were synthesized from 1-abietic acid (1) by using a carbon unit of its isopropyl group, via a Li-liq. NH_3 reduction of a dicarboxylic acid (6), an intramolecular carbenoid reaction of diazoketones (9) and subsequent cleavage of the resulting cyclopropyl ring of (10) and (11) with Li-liq. NH_3. d-Phyllocladene (18) was also synthesized from (1) by using two carbon units of its 13-side chain, via a stereo-selective hydrogenation (RuO_2) of an oxo diester (19) and a PPA-AcOH cyclization of a half ester (21), followed by a monothio-ketalization of a dioxo ester (25). Synthesis of 1-hibaene (48) from (1) was achieved by using a whole of the carbon units of its side chain, via a catalytic hydrogenation (RuO_2) of an oxoxy ester (29) and a methyl migration of a magnesium salt of a bromohydrin (41).
天然有機化合物討論会の論文
1976-09-20