Aromatic Osmacyclopropenefuran Bicycles and Their Relevance for the Metal-Mediated Hydration of Functionalized Allenes
Aromatic Osmacyclopropenefuran Bicycles and Their Relevance for the Metal-Mediated Hydration of Functionalized Allenes
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DOI：
10.1002/anie.201606839
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发表时间：
2016-10-24
影响因子：
16.6
通讯作者：
Onate, Enrique
中科院分区：
文献类型：
--
作者：
Batuecas, Maria;Castro-Rodrigo, Ruth;Onate, Enrique
芳香族锇环丙烷呋喃双环[OsTp{k（3）-C-1，C-2，O-（（CHCCHC）-H-1-C-2-C-2（OEt）O）}（（PPr 3）-Pr-1）] BF 4（Tp=三（1-吡唑基）硼酸酯）和[奥什（k（3）-C-l，C-2，O-（（CH 2 CCHC）-H-1-C-2（OEt）O）}（CO）（PiPr（3））（2）] BF 4，金属片段位于稠合的三元环和五元环之间的公共顶点，通过π-联烯中间体[OsTp（eta（2）-CH 2 = CCHCO 2 Et）（OCMe 2）（PiPr（3））] BF 4和[奥什（eta（2）-CH 2 = CCHCO 2 Et）（CO）（OH 2）（PiPr（3））（2）] BF 4合成了三个π-联烯衍生物，并用密度泛函理论计算了它们的芳香性。含[奥什（CO）（PiPr（3））（2）]（+）金属片段的双环是[奥什（CO）（OH 2）（2）（PiPr（3））（2）] BF 4催化的反马氏水合反应的关键中间体。
The aromatic osmacyclopropenefuran bicycles [OsTp{k(3)-C-1, C-2, O-((CHCCHC)-H-1-C-2-C-2(OEt) O)}((PPr3)-Pr-i)] BF4 (Tp= hydridotris(1-pyrazolyl) borate) and [OsH{k(3)-C-1, C-2, O-((CH2CCHC)-H-1-C-2(OEt) O)}(CO)(PiPr(3))(2)] BF4, with the metal fragment in a common vertex between the fused three-and fivemembered rings, have been prepared via the pi-allene intermediates [OsTp(eta(2)-CH2= CCHCO2Et)(OCMe2)(PiPr(3))] BF4 and [OsH(eta(2)-CH2= CCHCO2Et)(CO)(OH2)(PiPr(3))(2)] BF4, and their aromaticity analyzed by DFT calculations. The bicycle containing the [OsH(CO)(PiPr(3))(2)](+) metal fragment is a key intermediate in the [OsH(CO)(OH2)(2)(PiPr(3))(2)]BF4-catalyzed regioselective anti-Markovnikov hydration of ethyl buta-2,3-dienoate to ethyl 4-hydroxycrotonate.