カチオン性ロジウム錯体を触媒とする末端アルキンのヒドロゲルミル化 : 生活習慣病予防薬指向複素環の前駆体合成-2

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Synthesis of germylethene derivatives as precursors to germylated isoxazolines or isoxazolidines was investigated by the bis (cycloocta-1,5-diene) rhodium tetrafluoroborate-catalyzed hydrogermylation of several terminal acetylenes using triethylgermane. 2-Propyn-1-ol was subject to the hydrogermylation at 0℃ without dehydrogenative germylation between the alcohol and the hydrogermane giving an alkoxygermane to give a 99 : 1 mixture of trans-3-(triethylgermyl)-2-propen-1-ol and 2-(triethylgermyl)-2-propen-1-ol in a high yield. However, heating the reaction mixture including the catalyst was found to cause the isomerization of the trans-3-(triethylgermyl)-2-propen-1-ol to 3-germylpropanal. The hydrogermylation of 2-methyl-3-butyn-2-ol or 1-ethynylcyclohexanol proceeded at room temperature to give the respective transgermylethenes in high yields. !n the hydrogermylation of silylacetylene or germylacetylene, trans-2-germylated silylethene or germylethene was selectively produced, respectively. Styryltriethylgermanes (trans- or cis-form) or trans-styryltriethylsilane underwent the [2+3] dipolar cycloaddition with α-phenyl-N-methylnitrone to produce endo-4-metallated isoxazolidines in high yields.
2002-03-30