Bicyclo[6.3.0]undeca-1(11),2,4,6,8-pentaen-10-ylidene: An Aromatic Carbene with Ambiphilic Properties.,ChemPlusChem

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Bicyclo[6.3.0]undeca-1(11),2,4,6,8-pentaen-10-ylidene: An Aromatic Carbene with Ambiphilic Properties.
ChemPlusChem ( IF 3.0 ) Pub Date : 2017-03-22 , DOI: 10.1002/cplu.201700069
Hiroyuki Ishikawa ₁ , Jun-Ichi Nishida ₁ , John W Jones ₂ , Lawrence T Scott _{2,

3} , Takeshi Kawase ₁

Affiliation

The title carbene (4) was generated as a highly reactive species in solution by photoirradiation of 10-diazobicyclo[6.3.0]undecapentaene (5) using a high-pressure mercury lamp. Carbene 4 reacts with benzene to afford two isomeric adducts, 10-phenylbicyclo[6.3.0]undecapentaene (10) and tricyclo[9.3.03, 10 .0]heptadeca-1,3(10),4,6,8,12,14,16-octaene (11). The reactivity toward benzene is a characteristic of an electrophilic aromatic carbene analogous to cyclopentadienylidene 1. In contrast, the reaction of 4 with methanol produces 7-methoxybicyclo[6.3.0]undeca-1,3,5,8,10-pentaene (15). When [D1 ]methanol was employed as a reactant, the 10-deuterated analogue was formed. The results clearly indicate the formation of bicyclo[6.3.0]undecapentaenyl cation (7) as a novel 10 π-electronic compound by protonation of 4. Theoretical calculations indicate that the 2- and 7-positions of the cation have the largest positive charge in the cation. Moreover, the carbene was generated in the presence of tert-butyl hydroperoxide in aqueous tetrahydrofuran to afford azulene through oxidation of 7, followed by decarbonylation. The nucleophilic property of carbene 3 is similar to that of cycloheptatrienylidene 2. Thus, 4 can be regarded as a novel ambiphilic aromatic carbene.

中文翻译：

双环[6.3.0] undeca-1（11），2,4,6,8-戊烯-10亚烷基：具有两亲性质的芳族碳烯。

通过使用高压水银灯对10-重氮双环[6.3.0]十一碳五烯（5）进行光辐照，在溶液中生成了具有高反应性的标题碳烯（4）。碳4与苯反应生成两个异构体加合物，10-苯基双环[6.3.0]十一碳五烯（10）和三环[9.3.03，10 .0]庚烯-1,3（10），4,6,8,12 ，14,16-辛烯（11）。对苯的反应性是类似于环戊二烯1的亲电子芳烃的特征。相反，4与甲醇的反应产生7-甲氧基双环[6.3.0] undeca-1,3,5,8,10-戊烯（15 ）。当使用[D1]甲醇作为反应物时，形成10-氘代的类似物。结果清楚地表明，通过4的质子化，形成了作为新型10π电子化合物的双环[6.3.0]十一碳五烯基阳离子（7）。理论计算表明阳离子的2位和7位在阳离子中具有最大的正电荷。此外，在四氢呋喃水溶液中在叔丁基氢过氧化物的存在下生成卡宾，通过7的氧化，随后脱羰基，得到a。卡宾3的亲核性质类似于环庚三烯二烯的亲核性质。因此，4可以被认为是新型的两亲性芳烃卡宾。

更新日期：2017-03-22

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