Stability and Reactivity of 1,3-Benzothiaphosphole: Metalation and Diels鈥揂lder Chemistry

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• 作者：Joshua C. Worch ; Erich Hellemann ; Gabrielle Pros ; Chakicherla Gayathri ; Tomislav Pintauer ; Roberto R. Gil ; Kevin J. T. Noonan
• 刊名：Organometallics
• 出版年：2015
• 出版时间：November 23, 2015
• 年：2015
• 卷：34
• 期：22
• 页码：5366-5373
• 全文大小：390K
• ISSN：1520-6041

文摘

The synthesis and functionalization of the parent 1,3-benzothiaphosphole is reported. The phosphole could not be isolated, but the compound could be manipulated in solution to produce several new phosphorus compounds. Metalation of the 2-position using lithium diisopropylamide proceeded smoothly according to ³¹P NMR spectroscopy, and quenching with trimethylsilyl chloride resulted in the desired 2-(trimethylsilyl)-1,3-benzothiaphosphole. The P鈺怌 bond of the thiaphosphole was also explored as a dienophile in Diels鈥揂lder reactions with isoprene, 2,3-dimethylbutadiene, 2,3-dibenzylbutadiene, and cyclopentadiene. The fused-ring structures were fully characterized, and a solid-state molecular structure of the 2,3-dimethylbutadiene cycloadduct was obtained. Residual dipolar coupling (RDC) NMR experiments were used to assign major and minor products for the isoprene and cyclopentadiene adducts.