New formulas for organozincate chemistry
New formulas for organozincate chemistry
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DOI：
10.1021/ja973855t
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发表时间：
1998-05-27
影响因子：
15
通讯作者：
Sakamoto, T
中科院分区：
文献类型：
--
作者：
Uchiyama, M;Kameda, M;Sakamoto, T
作为一种新型的锌酸盐，我们设计了一系列新的有机锌衍生物Me 3 Zn（R）Li-2（R = Me，CN，SCN），它们可以由三甲基锌酸锂和阴离子如甲基锂、氰化锂和硫氰酸锂原位合成。我们研究了这些锌酸盐对卤素（或碲）-锌交换，迈克尔加成，碳锌化和环氧开环反应的反应性。基于其优异的化学产率和化学选择性，这些物种被认为是区别于普通的三有机锌酸盐，R3 ZnLi。利用H-1 NMR/拉曼/原位FTIR扩展的X射线吸收精细结构（EXAFS）光谱和密度泛函理论（DFT）研究了新设计的锌酸盐的结构。所有结果都有力地支持了这样一个事实，即这些新设计的锌酸盐是一个新的类别的锌酸盐物种。该观察结果也与新设计的锌酸盐与常规三有机锌酸盐相比具有更高和独特的反应性的事实相同。
As a new type of zincate, we designed various new organozinc derivatives, Me3Zn(R)Li-2 (R = Me, CN, SCN), which could be prepared in situ from lithium trimethylzincate and anion species such as methyllithium, lithium cyanide, and lithium thiocyanate. We investigated the reactivities of these zincates toward the halogen (or tellurium)-zinc exchange, Michael addition, carbozincation, and epoxide ring opening reactions. On the basis of their excellent chemical yields and chemoselectivities, these species were considered to be differentiated from ordinary triorganozincates, R3ZnLi. We also discuss the structure of the newly designed zincates using H-1 NMR/Raman/in situ FTIR-extended X-ray absorption fine structure (EXAFS) spectroscopic and the density-functional theory (DFT) theoretical studies. All results strongly support the fact that these newly designed zincates are a new category of zincate species. This observation is also identical with the fact that newly designed zincates have a higher and unique reactivity compared to the conventional triorganozincates.