Wee Meldon Yi-Shuo, Quek Shina, Wu Chi-Shiun, Su Ming-Der, So Cheuk-Wai
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 637371 Singapore.
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
J Am Chem Soc. 2024 May 29;146(21):14410-14415. doi: 10.1021/jacs.4c02807. Epub 2024 May 16.
Strained cyclic tetrylones are important synthons due to various synthetic applications. Connecting two cyclic tetrylone rings through a single shared quaternary group 14 element atom to form a spirocyclic molecule has been unexplored both theoretically and experimentally. The formation of a spirocyclic motif has been a synthetic challenge. In contrast, the reaction of amidinato disilicon(I) , (MeP)SiCl, and KC afforded π-delocalized spiro[3.3]heptasila-2,6-diylidone and tetrasilacyclobutadiene byproducts and . Compound is the smallest spirocyclic tetrylone derivative, which is composed of a σ-type lone pair and delocalized π bond in each all-silicon spirocyclic ring. The electronic property is supported by its coordination with a W(CO) moiety.
由于各种合成应用，张力环状四氢呋喃酮是重要的合成子。通过单个共享的第14族元素四价原子连接两个环状四氢呋喃酮环以形成螺环分子，在理论和实验上均未得到探索。形成螺环基序一直是一个合成挑战。相比之下，脒基二硅（I）、（MeP）SiCl和KC的反应产生了π离域的螺[3.3]庚硅-2,6-二亚基酮和四硅环丁二烯副产物 和 。化合物 是最小的螺环四氢呋喃酮衍生物，其在每个全硅螺环中由一个σ型孤对和离域π键组成。其电子性质由它与W(CO)部分的配位得到证实。
