133636-48-3

Upstream product

• 109-72-8 n-butyllithium 
• 19255-91-5 (2-chlorocyclopropane-1,1-diyl)dibenzene 
• 592-41-6 1-hexene 
• 693-03-8 n-butyl magnesium bromide 
• 22825-21-4 3,3-diphenylcyclopropene 
• 908093-98-1 diazodiphenylmethane 

Relevant academic research and scientific papers

Synthesis, structures, and catalytic reactivity of bis(N-heterocyclic carbene) supported diphenyldiazomethane and 1-azidoadamantane complexes of nickel

Diphenyldiazomethane reacts with Ni(NHC)2 (1, NHC = N-heterocyclic carbene) to afford complexes of the type (NHC)2Ni(κ1-N2CPh2) (3) in which the diazoalkane ligand is bound to the metal in an end-on κ

Copper(I)-catalyzed carbometalation of nonfunctionalized cyclopropenes using organozinc and grignard reagents

A highly efficient method was developed for the copper(I)-catalyzed carbometalation of various nonfunctionalized and functionalized cyclopropenes. Electrophilic trapping of the cyclopropylmetal intermediates gave multifunctionalized cyclopropanes.

DIKETIMINATO CU(I) AND CO(I) CARBENE CATALYSTS, AND CYCLOPROPANATION METHODS USING THEM

The present invention described herein employs employs Cu(I) complexes of an electron-rich, bidentate N,N-donor ligand (P-diketiminates) that react with both heteroatomcontaining a-substituted diazomethanes and ary1diazomethanes to yield a unique metal-carbene complex stabilized by two metal fragments that selectively reacts with alkenes. These examples are the first of isolable Cu-carbene complexes that react with alkenes to give cyclopropanes. Furthermore, electron-rich, bidentate N,N-donor ligands can be designed to impart stereo- and enantio-selectivity in the cyclopropanation of alkenes with diazoalkanes.

Discrete bridging and terminal copper carbenes in copper-catalyzed cyclopropanation

The Cu(I)/ β-diketiminate [Me2NN]Cu(η2- ethylene) (2) catalyzes the cyclopropanation of styrene with N 2CPh2 to give 1,1,2-triphenylcyclopropane in 67% yield. Addition of N2CPh2 to 2 equiv of 2 allows for the isolation of the dicopper carbene {[Me2NN]Cu}2(μ- CPh2) (3) in which the diphenylcarbene moiety is symmetrically bound between two [Me2NN]Cu fragments (Cu-C = 1,922(4) and 1.930(4) A) with a Cu-Cu separation of 2.4635(7) A. In toluene-d8 solution, 3 reversibly dissociates a [Me2NN]Cu fragment to give [Me2NN]Cu(toluene) and the terminal carbene [Me2NN]Cu= CPh2, Dicopper carbene 3 reacts with 3 equiv of styrene to give 1,1,2-triphenylcyclopropane and 2 equiv of [Me2NN] Cu(η2-styrene) within minutes, DFT studies with simplified ligands indicate a stronger Cu-C π-back-bonding interaction from two Cu(I) centers to the carbene acceptor orbital in a dicopper carbene than that present in a monocopper carbene. Nonetheless, the terminal carbene [Me 3NN]Cu=CPh2 (8) that possesses a p-methyl group on each β-diketiminato N-aryl ring may be isolated and exhibits a shortened Cu-C distance of 1,834(3) A, The stoichiometric cyclopropanation of styrene by 8 in 1,4-dioxane is first-order in both copper carbene 8 and styrene with activation parameters ΔH? = 10,4(3) kcal/mol and ΔS? = -32,3(9) cal/mol·K. In 1,4-dioxane, 8 decomposes to Ph 2C=CPh2 via first-order kinetics with activation parameters ΔH? = 21(1) kcal/mol and ΔS? = -8(3) cal/mol·K. Arene solutions of thermally sensitive terminal carbene 8 decompose to [Me3NN]-Cu(arene), which reacts with 8 still present in solution to give the more thermally stable {[Me3NN]Cu} 2-(μ-CPh2).

Palladium carbene cluster: synthesis, structure and reactivity

The first palladium carbene cluster, μ-tetrakis(diphenylmethyliden)-μ-tetraacetato-quadro-tetrapalladium (4Pd-Pd) Pd4(μ-CPh2)4(μ-OAc)4 (I), has been synthesized by substitution of diphenylcarbene ligands for CO-groups in μ-tetrakis(carbonyl)-μ-tetraacetat

OXIRANYLIDENE INTERMEDIATE IN THE REACTION OF TRANS-2-CHLORO-3-TERT-BUTYLOXIRANE WITH SODIUM PHENOXIDE

The reaction of trans-2-chloro-3-(t-butyl)oxirane with sodium phenoxide in acetonitrile to give trans-2-phenoxy-3-(t-butyl)oxirane involves α-elimination to give an oxiranylidene which undergoes a stereoselective stepwise addition of phenol to give produc