Fang Fan, Molino Andrew, Wentz Kelsie E, Folster Carlton P, Williams Jessica L, Siegler Maxime A, Klausen Rebekka S
Department of Chemistry, Johns Hopkins University, 3400 N. Charles St, Baltimore, Maryland, 21218, USA.
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts, 02139, USA.
Angew Chem Int Ed Engl. 2025 Aug 25;64(35):e202506054. doi: 10.1002/anie.202506054. Epub 2025 Jul 14.
We report the synthesis of five new examples of ladder cyclohexasilanes, possessing up to three consecutive fused rings and differing in relative ring fusion configuration and side chain structure. By coupling a 1,4-dipotassiooligosilyl dianion to a cyclohexasilane, we obtained bi- and tricyclic ladder cyclohexasilanes. Combined experimental and theoretical studies suggested that annulation could favor the cis configuration under kinetic control, while the trans configuration predominates under thermodynamic control. Computational studies show that with each additional ring in the trans-diastereomeric series, the predicted onset of light absorption shifts to longer wavelengths.
我们报道了五个新型梯形环己硅烷的合成,这些梯形环己硅烷具有多达三个连续的稠环,且在相对环稠合构型和侧链结构上有所不同。通过将1,4 - 二钾代低聚硅烷基二阴离子与环己硅烷偶联,我们得到了双环和三环梯形环己硅烷。结合实验和理论研究表明,在动力学控制下,环化有利于顺式构型,而在热力学控制下,反式构型占主导。计算研究表明,在反式非对映异构体系列中,每增加一个环,预测的光吸收起始波长就会移向更长波长。