DMAP-C-Me

A certain number of crystal structures have been solved of the donor DMAP-C-Me, 23 [11] (Fig.4) the acceptor BHTCNQ, 11 [13] (Fig.5), and of the methyl ester (AETCNQ, 27) of the acceptor HETCNQ, 12 [14] (Fig.6). TTie difference in conformation between AETCNQ... 

To date, no terminal unsupported Ln-imido complexes, Ln=NR, (Ln=Ce-Lu) have been isolated and characterized in the solid state, despite the comparative fertility of this area for related early TMs [83]. Structurally authenticated Ln-imido and -phos-phinidene complexes in the literature, typically prepared by the deprotonation of Ln—NHR and Ln—PHR precursors, form dimers in the solid state with bridging NR and PR fragments [84]. It is noteworthy that the transient existence of unsupported Ln=NR and Ln=PR linkages had previously been observed, though could not be isolated [95]. In the case of the RE, the first terminal Sc-imido complex, [Sc(=NDipp)(T -NacNac-K -A, A, A ")(DMAP)] (T -NacNac = (N(Dipp)C(Me) CHC(Me)N(CH2CH2NMe2) DMAP = 4-dimethylaminopyridine, 45), was recently prepared, which is stabilized by a bespoke tri-coordinate variant of the ubiquitous NacNac ligand [96]. 

BUO2CCI, A -methylmorpholine/EtsN H2C=C(Me)02Ca, V-methylmorpholine (r-BuOCO)20, py/(NH,)HC03 /-BuCOCl, EtjN <-BuCOCL DMAP, py... 

Scheme 16b. a) H2/Pt02/hexane b) NaBH4 c) Jones oxid. d) CH2= C(Me)MgBr, e) 03 Me2S f) SOCl2 g) MeLi h) l(S)-(-)-camphanyl chloride/DMAP/Et3N HPLC. 

Ac, acetyl AIBN, azobis(isobutanonitrile) All, allyl AR, aryl Bn, benzyl f-BOC, ferf-butoxycarbonyl Bu, Butyl Bz, benzoyl CAN, ceric ammonium nitrate Cbz, benzyloxycarbonyl m-CPBA, m-chloroperoxybenzoic acid DAST, diethylaminosulfur trifluoride DBU, l,8-diazabicyclo[5.4.0]undec-7-ene DCC, /V. /V - d i eye I oh e x y I c ar bo -diimide DCM, dichloromethyl DCMME, dichloromethyl methyl ether DDQ, 2,3-dichloro-5,6-dicyano-l,4-benzoquinone DEAD, diethyl azodicarboxylate l-(+)-DET, L-(+)-diethyl tartrate l-DIPT, L-diisopropyl tartrate d-DIPT, D-diisopropyl tartrate DMAP, 4-dimethylaminopyridine DME, 1,2-dimethoxyethane DMF, /V./V-dimethylformamide DMP, 2,2-dimethoxypropane Et, ethyl Im, imidazole KHMDS, potassium hexamethyldisilazane Me, methyl Me2SO, dimethyl sulfoxide MOM, methoxymethyl MOMC1, methoxymethyl chloride Ms, methylsulfonyl MS, molecular sieves NBS, N-bromosuccinimide NIS, /V-iodosuccinimide NMO, /V-methylmorpho-line N-oxide PCC, pyridinium chlorochromate Ph, phenyl PMB, / -methoxvbenzyl PPTs, pyridiniump-toluenesulfonate i-Pr, isopropyl Py, pyridine rt, room temperature TBAF, tetrabutylammonium fluoride TBS, ferf-butyl dimethylsilyl TBDMSC1, f-butylchlorodimethylsilane Tf, trifhioromethylsulfonyl Tf20, trifluoromethylsulfonic anhydride TFA, trifluoroacetic acid THF, tetrahydrofuran TMS, trimethylsilyl TPAP, tetra-n-propylammonium perruthenate / -TsOH. / -toluenesulfonic acid... 

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