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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT

We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.

2D 7Li,15N heteronuclear shift correlation through scalar coupling has successfully been applied to several lithium organyls consisting of polydentate N ligands such as N,N,N,N-tetramethylethylenediamine (tmeda), N,N,N,N,N′-pentamethyldiethylentriamine (pmdta) and (-)-sparteine. Structural insights on the conformation of benzyllithium× pmdta (5) in a toluene solution and the strength of ion pairing in combination with PGSE NMR measurements, 1H,1H-NOESY and 1H,7Li-HOESY experiments are presented. By studying in detail the formation of 5 in solution, a transient species has been observed for the first time and assigned to a pre-complex of nBuLi and pmdta. In addition, the solution behaviour of the complex formed between benzyllithium and (-)-sparteine (8) has been studied by PGSE and multinuclear NMR spectroscopy. The straightforward synthesis and first applications in asymmetric lithiations are also reported, which show that the new system benzyllithium×(-)- sparteine (8) provide poorer enantioselective induction than the classical nBuLi×(-)-sparteine (6). The results were supported by deprotonation experiments confirming that the formation of 8 relies on two relevant factors, namely temperature and lithiating reagent. The existence of 8 may thus interfere with the asymmetric induction when the system nBuLi× (-)-sparteine is used in the enantioselective deprotonations of N-Boc-N-(p-methoxyphenyl)- benzylamine conducted in toluene. To pair or not to pair: 2D 7Li,15N heteronuclear shift correlation has been applied to several lithiumorganyls consisting of polydentate N ligands such as N,N,N,N-tetramethylethylenediamine, N,N,N,N,N′- pentamethyldiethylentriamine and (-)-sparteine. In combination with other spectroscopic techniques, details on the formation of the lithiumorganyl- polyamine adducts the strength of ion pairing in solution have been explored (see figure). Copyright

The formation of reactive carbanions in Grignard reagents was discussed. Inter- and/or intramolecular migrations of organotin and organosilicon groups were also studied. Results showed that the high percentage of rearrangement reactions proves that the anionic species are not located on a minor pathway.

Homologous compounds of the linalool type R(CH3)2El-OH (with R=C6H5CH2 and C6H5CH2CH2) as well as their derivatives R(CH3)2El-OCH3 and 2O show, in dependence of El=C, Si, Ge and Sn partly similar, but sometimes very different characteristics of odor.Unexpected are high qualities of fragrance with El=Ge, whereas derivatives with El=Sn remain scentless, obviously owing to polymerization.Noteworthy are the strong differences of odor in the system C6H5CH2El(CH3)3 from C via Si and Ge up to Sn, standing fully contrary to the postulation of Amoore whereupon smell qualities are only controlled by size and shape of molecules.C6H5CH2Sn(CH3)2OH(A1Sn) crystallizes as poly-μ-hydroxo-benzyldimethyltin with an one dimensional Sn-O-Sn-O chain (Sn-O 2.17(9) and 2.29(9) Angstroem) in the monoclinic space group C2 (a=12.696(4), b=4.181(2), c=10.626(3) Angstroem and β=106.8(3) deg).

The reaction of bis(trimethylstannyl) sulphide and sodium with toluene, m-xylene, p-xylene and thioanisole gives stannylation at the methyl group whereas anisole was stannylated at the aromatic nucleus with very high ortho selectivity

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The reactions of eleven alkyl chlorides and bromides with trimethyltinsodium have been examined.It has been found that primary and secondary halides react smoothly and rapidly to provide good yields of substitution products in THF and TG at Oo.The reaction is less satisfactory for allyl bromide and unsatisfactory for cinnamyl chloride and tertiary halides.Trimethyltinsodium and 2-chlorobutane react with second order kinetics.Relative reactivities of the halides have been determined in the two solvents and are discussed.Lithium, sodium and potassium as counterions yielded the same results in the reaction of the trimethyltinalkils with primary, secondary and tertiary butyl bromides in THF.

Several novel metal-carbonyl complexes of tin-containing arene ligands of the general formulas (CH3)nSn(C6H5) 4-n·mM(CO)3 (where n = 2 or 3, m = 1 or 2, and M = Cr or Mo), [(CH3)