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首页> 外文期刊>J.Chem.Soc., Perkin Transaction 2 >Protonation studies on epimeric homoallylic adamantylideneadamantyl alcohols, 4-methyleneadamantylideneadamantane, adamantylideneadamantane (AdAd) and sesquihomoadamantene, and reaction of AdAd and sesquihomoadamantene with NO2+BF4− and PhI(OH)OTs: a stable-ion NMR and theoretical (GIAO-NMR) study
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Protonation studies on epimeric homoallylic adamantylideneadamantyl alcohols, 4-methyleneadamantylideneadamantane, adamantylideneadamantane (AdAd) and sesquihomoadamantene, and reaction of AdAd and sesquihomoadamantene with NO2+BF4− and PhI(OH)OTs: a stable-ion NMR and theoretical (GIAO-NMR) study

机译：对差向异构体均烯丙基金刚烷金刚烷醇，4-亚甲基金刚烷金刚烷，金刚烷金刚烷（AdAd）和倍半金刚烷的质子化研究以及AdAd和倍半金刚烷与NO2 + BF4-和PhI（OH）OTs的反应：稳定离子NMR和理论研究（GIAO）

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Under stable-ion conditions, the “pseudo-axial” homoallylic alcohol 1-ax is protonated at the Adu0001 u0001Ad double-bondnand the resulting carbocation undergoes rapid cyclization to produce the oxonium ion 9Hu0002 as the only observablenspecies, which on quenching furnishes the cyclic ether 9. In contrast, protonation of the “pseudo-equatorial”nhomoallylic alcohol 1-eq gave a persistent homoallylic cation 1au0002. Protonation of the methylene-substitutednderivative 8 gave a 5 : 1 mixture of two carbocations, in which the minor ion is homoallylic 8aHu0002. Adamantyl-nideneadamantane Adu0001 u0001Ad 5 reacts with FSO3H–CH2Cl2 to give the previously observed 5Hu0002 (as a rapidly equilibratingnpair of carbocations), together with the oxonium ion 6Hu0002. The outcome of the reaction of Adu0001 u0001Ad with NO2BF4,nNOBF4 and with PhI(OH)OTs is the same, in all cases producing the spirocyclic ketone 6. Sesquihomoadamantene 7nis protonated in FSO3H–SO2ClF and the initially formed carbocation (not observed) rapidly rearranges to 5Hu0002.nCompound 7 also reacts with NO2BF4, and TFA–CH2Cl2 to produce the spirocyclic ketone 6 and 5, after quenching.nWith PhI(OH)OTs the recovered material is 7 itself plus PhI. For comparison, the homoallylic carbocations 1au0002,n8aHu0002, their skeletally rearranged allylic cations 1bu0002, 8cHu0002, and the oxonium ions 9Hu0002 and 6Hu0002 were studiedncomputationally by GIAO-NMR at the BLYP/6-31G(d)//BLYP/6-31G(d) level.
机译：在稳定离子条件下，“伪轴”均烯丙基醇1-ax在双键Adu0001 u0001Ad上质子化，生成的碳正离子经过快速环化反应生成氧离子9Hu0002，这是唯一可观察到的物种，在淬灭后会提供环状醚。 9.相反，“伪赤道”正烯丙基醇1-eq的质子化得到持久的均烯丙基阳离子1au0002。亚甲基取代的n-衍生物8的质子化得到两个碳正离子的5∶1混合物，其中次要离子是同质的8aHu0002。金刚烷基-亚胺基金刚烷Adu0001 u0001Ad 5与FSO3H–CH2Cl2反应，生成先前观察到的5Hu0002（作为碳正离子的快速平衡对），以及氧离子6Hu0002。 Adu0001 u0001Ad与NO2BF4，nNOBF4和PhI（OH）OTs的反应结果相同，在所有情况下均产生螺环酮6。倍半金刚烷7nis在FSO3H-SO2ClF中质子化，并且最初形成的碳正离子（未观察到）迅速重排。到5Hu0002。n化合物7也与NO2BF4和TFA-CH2Cl2反应，在淬灭后产生螺环酮6和5。n用PhI（OH）OTs回收的物质是7本身加上PhI。为了进行比较，通过GIAO-NMR在BLYP / 6-31G（d）// BLYP / 6-31G（）上进行了均方碳正离子1au0002，n8aHu0002，其骨架重排的烯丙基阳离子1bu0002、8cHu0002和氧离子9Hu0002和6Hu0002的研究。 d）水平。

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