NaN SiMe

Scheme 2.3 Illustration of some organic reactions using NaHMDS (NaN(SiMe-,)2)...

F. Mixed Cyanocarbonyl Metalates Prepared from Metal Carbonyl Derivatives and NaN(SiMes)2. 38... 

In the cases of the olefin-bridged, iron complexes (OC)3Fe(olen)Fe(CO)3 (olen = cyclooctatetraene, l,l -di-2,4-cyclohexadienyl, 1, l -di-2,4-cyclo-heptadienyl), we have again shown that reaction with NaN(SiMes)2 leads exclusively to the corresponding monocyano complexes [(OC)[Pg.41]

Ziegler and his cowoikers modified the reaction conditions by conducting the reaction under high dilution conditions and using a soluble base in ether as the solvent. Sodium methylanilide was reported to be the best base6 but an example has been reported in which this gave unexpected products.212 A variety of other bases have been used more recently and a comparison of LDA, LiNEt2 and NaN(SiMe.i)2 has been made.213... 

A related enolate complex [Na Pr 2PC(H)=C(0)Ph ]4 has been prepared by deprotonation of the ketone Pr PCH2C(0)Ph with NaN (SiMes)2 170). In the solid state this complex adopts a cubane-type structure with a Na404 core. Each ligand bridges opposite edges of the cube, forming a five-membered chelate ring at each sodium. The Na-P distance in this complex of 2.852(2) A is short in comparison to other similar contacts. 

Caution NaN(SiMe can react violently with moisture and must be stored and handled under an inert atmosphere. 

Azides, Diazoalkanes, Diazirines, Azo-compounds, and Azines. Fluorinated alkanoyl azides have been dealt with already in other sections, mainly that concerned with isocyanates (see pp. 227,228, and 229). The azides CHFa Ns, (CFs)2C(N3) O SiMes, and (CF3)sC(Ns) O SOsO have been obtained from the reaction systems CHFsCl-NaNs-alkali-HsO-dioxan, (CF3)2CO-Me8Si N3,i and (CF3)2C(Ns) ONa-S2O5CIX (X = F or Cl), respectively. Eleven 2-azido-3,3>difluorocyclobutenes have been synthesized as indicated in Scheme 49 and converted thermally or photo-chemically into the corresponding 2,2-difluorocyclopropanes decomposition of the 1-cyano- and 1-methoxycarbonyl-cyclobutenes in the presence of electron ri( aromatics gave pyrrole derivatives. These results have been discussed in terms of the mechanistic pathways contained in Scheme SO Neber rearrangement with EtsN... 

Stabilized Cu(I) in the form of its iV-heterocyclic carbene (NHC) complex, e.g., (SIMes)CuBr (SIMes = iV,7V -f>is(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene), and the eyclohexyl analog [(ICy)2Cu]PF6, catalyzes click reactions very well in aqueous /-butanol, and even better in water alone. Low conversions were noted in nonaqueous solvents such as tetrahydrofuran (THF), /-BuOH, and dichloromethane (DCM). Starting from an alkyl bromide, triazoles could be smoothly generated by m situ conversion to the corresponding azide (aqueous NaNs) followed by copper-catalyzed cycloaddition. This is but one example of the potential for combining several steps in a single flask that culminates with a click reaction vide infra). The... 

---