化学
烯烃纤维
区域选择性
部分
药物化学
催化作用
乙炔
选择性
铜
替代(逻辑)
硅烷化
立体化学
磷酸盐
有机化学
计算机科学
程序设计语言
作者
Yuichi Kobayashi,Takayuki Hirotsu
出处
期刊:Synlett
[Georg Thieme Verlag KG]
日期:2022-10-26
卷期号:34 (02): 159-162
被引量:2
摘要
Abstract (S)-Nyasol was selected as a target to demonstrate the efficiency of a copper-catalyzed substitution of secondary propargylic phosphates. The key phosphate (R)-TBDPSO(CH2)2CH[C≡C(C6H4-4-OTBS)]OP(O)(OEt)2 was synthesized from TBDPSO(CH2)2CO2H in four steps. Substitution of the phosphate with 4-TBSOC6H4MgBr in the presence of CuBr·Me2S as a catalyst in THF–DME proceeded with both stereo- and regioselectivity at the propargylic position. All the silyl groups in the propargylic product, TBDPSO(CH2)2CH[C≡C(C6H4-4-OTBS)](C6H4-4-OTBS) were removed, and the acetylene bond was reduced by using active Zn to produce the cis-olefin. Finally, the HO(CH2)2 moiety was converted into CH2=CH, giving (S)-nyasol with 97% cis selectivity, 94.5% ee, and >99% enantiospecificity. Similarly, dihydronyasol was synthesized through hydrogenation of the substitution product, followed by construction of the terminal olefin.
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