Dzhemilev reaction

Scheme 41 Key applications of cyclometallation reaction (Dzhemilev reaction)...

D yakonov VA (2010) Dzhemilev reactions in organic and organometallic synthesis. NOVA Science, New York... 

Dzhemilev and Tolshkov et al. have studied the influence of phosphines and addi-hves in the hydroaminahon of 1,3-butadiene with morpholine catalyzed by the Ni(acac)2/phosphine/AlEt3/ additive (1/3/3/10) system [180]. With CF3CO2H as additive, the reaction is highly selective (>93%) for the formahon of l-(N-morpholino)-2-butene (>80% yield) by using P(w-Bu)3 or P(OEt)3 as phosphine. With the same system and PCI3 as phosphine, a mixture of 3-(N-morphoHno)-l-butene (70%) and l-(N-morpholino)-2-butene (30%) is formed (TOE = 21 h ). 

Dzhemilev UM, Kunakova RV, Sidorova VV (1987) Joint catalytic activation of C02 and NH2 in reaction with butadiene under the action of palladium complexes. Russ Chem Bull 36 362-364... 

The first report on carbomagnesation catalyzed by zirconium was made by Dzhemilev et al., who carried out the reaction by taking olefin, EtMgZ [Z, see Eq. (17)], and a catalytic amount of Cp2ZrCl2 at near room temperature to obtain 2-ethylalkylmagnesium reagent with a good selectivity [Eq. (17) 6]. 

The zirconium-catalyzed carbometalation reaction has been developed from the initial observation by Dzhemilev in 1983 that Cp2ZrCl2 (1) catalyzes the addition of ethyl-magnesium halide to unactivated alkenes [104-106]. A plausible mechanism for this carbometalation involves zirconocene and zirconacyclopentane species (Scheme 6.5) [107-109]. Diastereo- and enantioselective carbomagnesation is accomplished by use of chiral fl .sa-zirconocene derivative [110]. 

Dzhemilev et al. (1991) conducted an interesting investigation on the yield of cycloheptatriene formed in the reaction of benzene with diazomethane with various catalysts. The yield decreases in the presence of transition metal complexes in the series Rh-C (100<7o), Rh2(CF3COO)4 (57q/o), CuCl (39< o), CuBr (37<7o), Rh2(CH3COO)4 (17< o), activated charcoal (15 /o). Toluene, biphenyl, and dimethyl-benzenes yield mixtures of the corresponding regioisomeric cycloheptatriene derivatives in 82-98 yield. With naphthalene, cyclopropanation took place in the 1,2-position only (98< o). The benzonorcaradiene formed resisted isomerization to benzocycloheptatriene. 

RSO2H RSOjCHjOH Michael additions and Mannich reactions involving RSO2HI F. Manescalchi, M. Orena, and D. Savoia, Synthesis, 1979,445 [benzenesulphinate salts of polymer-bound cations, with alkyl halides] U. M. Dzhemilev, R. V. Kunakova, R. L. Gaisin, and G. A. Tolstikov, Izv. Akad, Nauk SSSR, Ser. Khitn., 1979,2702 U. M. Dzhemilev, R. V. Kunakova,... 

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