26149-14-4

Upstream product

• 507-20-0 tertiary butyl chloride 
• 86-29-3 Diphenylacetonitrile 
• 38442-51-2 tert-butylmercury chloride 
• 119072-55-8 tert-butylisonitrile 
• 1871-76-7 diphenylacetic acid chloride 
• 90-99-3 diphenylchloromethane 
• 908093-98-1 diazodiphenylmethane 
• 71-43-2 benzene 
• 18802-83-0 diphenylacetonitrile anion 

Relevant academic research and scientific papers

Carbenerhodium complexes of the half-sandwich-type: Synthesis, substitution, and addition reactions

A series of carbenerhodium(I) complexes of the general composition [(η5-C5H5)Rh(=CRR′)(L)] (2a-2i) with R = R′ = aryl and L = SbiPr3 or PR3 has been prepared from the square-planar precursors trans-[RhCl(=CRR′)(L)2] and NaC5H5 in excellent yields. Reaction of the triisopropylstibane derivative 2a, which contains a rather labile Rh-Sb bond, with CO, PMe3, and CNR (R = Me, CH2Ph, tBu) leads to the displacement of the SbiPr3 ligand and affords the substitution products [(η5-C5H5)Rh-(=CPh2)(L)]. (3-7). In contrast, treatment of the triisopropylphosphane compound 2c with CO and CNtBu leads to the cleavage of the Rh=CPh2 bond and gives besides [(η5-C5H5)Rh(PiPr3)(L)] (10, 12) by metal-assisted C-C coupling diphenylketene Ph2C=C=O (11) or the corresponding imine Ph2C=C=NtBu (13). While the reaction of 2a, c with C2H4 yields [(η5-C5H5)Rh(C2H4) (L)] (14, 15) and the trisubstituted olefin Ph2C=CHCH3 (16), treatment of 2a, c with RN3 leads to the cleavage of both the Rh-EiPr3 and Rh=CPh2 bonds and gives the chelate complexes [(η5-C5H5)-Rh(κ2-RNNNNR )] (19, 20). The substitution products 3 (L = CO) and 4 (L = PMe3) react with an equimolar amount of sulfur or selenium by addition of the chalcogen to the Rh=CPh2 bond to generate the complexes [(η5-C5H5) Rh-(κ2-ECPh2)(L)] (21-24) with thio- or selenobenzophenone as ligand. Similarly, treatment of 3 with CuCl affords the unusual 1:2 adduct [(η5-C5H5)(CO)Rh-(μ-CPh2) (CuCl)2] (25), which reacts with NaC5H5 to form [(η5-C5H5)(CO)Rh(μ-CPh2)Cu (η5-C5H5)] (26). The molecular structures of 3 and 22 have been determined by X-ray crystallography.

A new family of carbenerhodium(i) complexes: Ligand variation as the key to success

A synthetic methodology to obtain square-planar carbenerhodium(I) complexes of the general composition trans-[RhCl(=CRR')(L)2] where L is a tertiary phosphane, arsane, or stibane has been developed. The starting material trans-[RhCl(C2H4)(SbiPr3)2] (3) reacts with diazoalkanes RR'CN2 [RR' = Ph2, Ph(C6H4X), (C6H4X)2, Ph(CF3), C12H8] under mild conditions to give the compounds trans-[RhCl(=CRR')(SbiPr3)'2] (4-11) almost quantitatively. On treatment of 3 with EtO2CCHN2 and PhC(N2)C(O)R, the olefin rhodium and diazoalkanerhodium compounds trans[RhCl{(E)-C2H2(CO2Et)2}(SbiPr3)2] (12) and trans-[RhCl{N2C(R)C(O)Ph}(Sb-iPr3)2] (13, 14) are obtained instead of carbene complexes. Displacement of the SbiPr3 ligands in 4 (R=R'=Ph) by PiPr3, PiPr2Ph, PiPrPh2, PPh3, PPh2Me, AsiPr3, and SbEt3 leads to the corresponding carbene complexes trans-[RhCl-(=CPh2)(L)2] (15-21) in high yields. The results of the X-ray crystal structure analyses of 4 and 15 (L = PiPr3) illustrate that the different donor-acceptor properties of SbiPr3 and PiPr3 have little influence on the Rh-C bond length. The reactions of 4 and 15 with CO and CNtBu afford, by metal-assisted C-C coupling, diphenylketene Ph2C=C=O (23) and the corresponding imine Ph2C=C=NtBu (26). On treatment of 4 and 15 with ethene, however, two different olefinic products, 3,3-diphenyl-1-propene (31) and 1,1-diphenyl-1-propene (32), are formed. Compound 15 reacts with KBr, NaOPh, and NaC5H5 by substitution of the chloride to give trans-[RhBr(=CPh2)-(PiPr3)2] (33), trans-[Rh(OPh)(=CPh2)-(PiPr3)2] (34) and [C5H5Rh(=CPh2)-(PiPr3)] (35), and with HCl by oxidative addition toyield [RhCl2(CHPh2)-(PiPr3)2] (36).

Carbene Formation and Transfer at a Dinickel Active Site

The synthesis and reactivity of a dinickel bridging carbene is described. The previously reported [i-PrNDI]Ni2(C6H6) complex (NDI = naphthyridine-diimine) reacts with Ph2CN2 to generate a metastable diazoalkane adduct, which eliminates N2 at 60 °C to yield a paramagnetic Ni2(μ-CPh2) complex. The Ni2(μ-CPh2) complex undergoes carbene transfer to t-BuNC via an initial isonitrile adduct, which upon heating releases free t-BuNCCPh2. On the basis of this sequence of stoichiometric reactions, a catalytic carbene transfer reaction is demonstrated.

Palladium(II)-catalyzed cross-coupling of diazo compounds and isocyanides to access ketenimines

Diazo compounds and isocyanides are reactive functionalities and valuable building blocks commonly utilized in organic synthesis. Their cross-coupling for the synthesis of useful isolable ketenimines remains an unsolved challenge in synthetic chemistry. Herein, we report a general method for the preparation of ketenimines via a palladium-catalyzed cross-coupling of easily accessible diazo compounds with isocyanides. The reaction benefits from the use of readily available starting materials, a wide substrate scope, high functional group tolerance, and a high yield in products, and the resultant ketenimines are amenable to further functionalization. Experimental findings and DFT calculations unambiguously corroborate the initial formation of a Pd(II)? isocyanide complex as the active catalytic species, which enables the cross-coupling reaction via a migratory insertion of Pd(II)? carbene into isocyanide, with evidence suggesting that the oxidation state of Pd(II) remains unchanged during the reaction.

Nickel-Catalyzed Formal Aminocarbonylation of Secondary Benzyl Chlorides with Isocyanides

Phenylacetamides represent versatile feedstocks in synthetic chemistry, widely existing in drug molecules and natural products. Herein, we disclose a nickel-catalyzed formal aminocarbonylation of secondary benzyl chlorides with isocyanides yielding α-substituted phenylacetamide with steric hindrance, which is synthetically challenging via palladium-catalyzed aminocarbonylation. The reaction features wide functional group tolerance under mild conditions, highlighted by the tolerance of various aromatic halide (-Cl, -Br, -I) and heteroaromatic rings (pyridine and pyrazine).

Palladium-Catalyzed Migratory Insertion of Isocyanides for Synthesis of C-Phosphonoketenimines

An efficient method for the synthesis of C-phosphonoketenimines through palladium-catalyzed migratory insertion of isocyanides has been developed for the first time. This procedure tolerates wide functional groups and has a good atom economy. Further tran

New synthesis of diphenyl-N-(substituted)ketenimines from diaminophosphonium diazaylides

Diaminophosphonium diazaylides 2 react under mild conditions with diphenylacetyl chloride, to afford diphenyl-N-(substituted)ketenimines 4 or, depending on the case, their transformation products: either the tautomer 8, or the dimer 9. The general reactio

A New and Facile Synthesis of Ketene Imines and Their 2-Iminoazetidine Dimer from Nitriles via Their Nitrilium Salts

A new one-pot synthesis of N-tert-butylketene imines 3 was accomplished on the basis of the reaction of N-tert-butylacetonitrilium tetrachloroferrate 2 with an organic base such as triethylamine or N-trisubstituted amidine 4.The α-hydrogen in 2 is particu

THE REACTION OF CARBANIONS WITH TERT-BUTYL RADICALS

The SRNl free radical chain reaction of Me3CHgCl with nitronate -O2N=C(R1)(R2)> and phenone enolate -)=C(R1)(R2)> anions yields the C-alkylation products 1)(R2)NO2, PhCOC(R1)(R2)CMe3>.Competitive reactions between pairs of anions demonstrate that as the basicity of the anion increases the reactivity toward Me3Cat first increases and then decreases.An inverted reactivity order is also observed with phenylacetonitrile anions.In early transition state reactions, the nucleophilic character of the tert-butyl radical apparently controls the reactivity by virtue of a transition state involving transfer of the electron from radical to the LUMO of the resonance stabilized anion.