181281-13-0Relevant articles and documents
Development of highly chemoselective bulky zincate complex, tBu 4ZnLi2: Design, structure, and practical applications in small-/macromolecular synthesis
Furayama, Taniyuki,Yonehara, Mitsuhiro,Arimoto, Sho,Kobayashi, Minoru,Matsumoto, Yotaro,Uchiyama, Masanobu
supporting information; experimental part, p. 10348 - 10356 (2009/10/10)
We present full details of the unique reactivities of the newly developed dianion-type bulky zincate, dilithium tetra-ferf-butylzincate (tBu 4ZnLi2). With this reagent, halogen-zinc exchange reaction of variously functionalized haloaromatics and anionic polymerization of N-isopropylacrylamide (NIPAm)/styrene with excellent chemoselectivity were realized. Halogen-zinc exchange reaction followed by electrophilic trapping with propargyl bromide provided a convenient route to functionalized phenylallenes, particularly those with electrophilic functional groups (such as cyano, amide and halogens). Spectral and computational studies of the structure in the gas and liquid phases indicated extraordinary stabilization of this dianion-type zincate by its bulky ligands.
New formulas for organozincate chemistry
Uchiyama, Masanobu,Kameda, Mitsuyoshi,Mishima, Osamu,Yokoyama, Nobuko,Koike, Minako,Kondo, Yoshinori,Sakamoto, Takao
, p. 4934 - 4946 (2007/10/03)
As a new type of zincate, we designed various new organozinc derivatives, Me3Zn(R)Li2 (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 1H NMR/Raman/in situ FTIR/extended X-ray absorption the 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.
