72090-05-2

Upstream product

• 673-32-5 1-Phenylprop-1-yne 
• 80150-91-0 C₁₂H₁₉⁽²⁾HN⁽¹⁺⁾*Cl^(1-) 
• 80150-89-6 C₁₂H₁₉⁽²⁾HN⁽¹⁺⁾*Cl^(1-) 
• 80150-89-6 C₁₂H₁₉⁽²⁾HN⁽¹⁺⁾*Cl^(1-) 
• 60468-24-8 (2-deuterio-2-propenyl)benzene 
• 71001-35-9 (2-bromoprop-1-en-1-yl)benzene 

Relevant academic research and scientific papers

Visible light-mediated metal-free double bond deuteration of substituted phenylalkenes

Various bromophenylalkenes were reductively photodebrominated by using 1,3-dimethyl-2-phenyl-1H-benzo-[d]imidazoline (DMBI) and 9,10-dicyanoanthracene. With deuterated DMBI analogs (the most effective was DMBI-d11), satisfactory to excellent isotopic yields were obtained. DMBI-d11 could also be regenerated from the reaction mixtures with a recovery rate of up to 50%. The combination of the photodebromination reaction with conventional methods for bromoalkene synthesis enables sequential monodeuteration of a double bond without the necessity of a metal catalyst. This journal is

Catalytic Semireduction of Internal Alkynes with All-Metal Aromatic Complexes

A simple catalytic method involving all-metal aromatic frameworks as precatalysts ensures an efficient route to (Z)-alkenes. Aromatic triangular palladium clusters were used to reduce internal alkynes without any trace of the formation of alkane side products. These trinuclear complexes provide a catalytic system that parallels the activity and selectivity of their best mononuclear peers, and the catalyst likely operates through complementary mechanisms.

Z-selective semihydrogenation of alkynes catalyzed by a cationic vanadium bisimido complex

Early metal gets the H: Under 1 atm of H2, the vanadium complex 1 (PFTB=perfluoro-tert-butoxide) catalytically semihydrogenates alkynes to Z alkenes. Synthetic and DFT studies, in combination with H2/D 2 and NMR experiments, indicate that H2 is activated by 1,2-addition to 1. Upon insertion of an alkyne into the V-H bond of A, the product alkene and 1 are generated by the 1,2-α-NH-elimination of the alkenyl ligand.

Stoichiometric Reactions of Nonconjugated Dienes with Zirconocene Derivatives. Further Delineation of the Scope of Bicyclization and Observation of Novel Multipositional Alkene Regioisomerization

The reaction of n-Bu2ZrCp2 with nonconjugated dienes containing substituted vinyl groups can lead to either bicyclization or the formation of conjugated diene-zirconocenes via multipositional regioisomerization.

Organometallic compounds of Group III XLIV. Molecular hydrogen and aluminium hydride transfers mediated by nickel(0) complexes: the intermediacy of nickel hydrides in the Ziegler nickel effect

In investigating the possible mechanistic similarity between dihydrogen and aluminium hydride transfers to unsaturated hydrocarbons, the catalytic action of nickel(0) complexes on such transfers was investigated in detail.For dihydrogen transfers the tendency of dihydroaromatics to disproportionate into tetrahydroaromatic and aromatic hydrocarbons was evaluated for 1,2- and 1,4-dihydrobenzenes, 1,2- and 1,4-dihydronaphthalenes and 9,10-dihydroanthracene toward (Cod)2Ni, Bpy(Cod)Ni and (Et3P)4Ni.The catalyzed disproportionation, which proceeded with decreasing rate in the order, 1,4-C6H8 > 1,2-C6H8 > 1,2- and 1,4-C10H10 >> 9,10-C14H12, was interpreted in terms of the formation of intermediate allylic nickel hydrides.The study of aluminum hydride transfer to unsaturated hydrocarbons was carried out by letting organoaluminum alkyls or hydrides interact with nickel(0) complexes.Three different reactions were observed: (1) nickel-catalyzed olefin formation from R3Al; (2) nickel-catalyzed hydroaluminum from R2AlH and unsaturated hydrocarbons; and (3) stoichiometric reaction of nickel(0) compounds and LiAlH4 or R2AlH to from aluminum nickelides (LiAlH2Ni).The rates, stereochemistry, regiochemistry and deactivation of the thermal and nickel-catalyzed hydroaluminations of alkenes and alkynes were compared, in order to learn about the most probable catalytic carriers in such nickel catalysis.The foregoing lines of evidence on how nickel(0) interacts with organoaluminum compounds are brought together in formulating a new, comprehensive mechanism for the Ziegler Nickel Effect.In this novel molecular view, the catalytic carriers in the Nickel Effect are dialkylaluminum nickel hydrides.Seen in this light, dihydrogen and aluminum hydrogen transfers have more than just a formal similarity; both processes proceed by nickel hydrides, which are formed by way of oxidative insertions, into a C-H and an Al-H bond, respectively.

THE EFFECT OF PHENYL SUBSTITUENTS ON ELIMINATION STEREOCHEMISTRY: A MECHANISTIC MANIFOLD IN ALKOXIDE PROMOTED DECOMPOSITION OF 1-PHENYL-1-PROPYLTRIMETHYLAMMONIUM ION

Reactions of the positionally isomeric 1-phenyl-1-propyl (I) and 1-phenyl-2-propyltrimethylammonium (II) ions with CH3OK - CH3OH, t-C4H9OK - t-C4H9OH and t-C4H9OK - C6H6 systems have been investigated with aid of the deuterated analogues erythro-2-D-I, threo-2-D-I, 1-D-I and threo-1-D-II.At least five mechanistic components (anti-β-elimination, syn-β-elimination, α',β-elimination, Sommelet-Hauser rearrangement and SN2 substitution) have been found to participate in the reaction of the quaternary compound I, in proportions varying greatly with base-solvent combination.The corresponding reactions of the isomeric compound II proceeded in a more simple manner, withount the intervention of ylide pathways in the olefin as well as in the amine formation.The stereochemistry of β-elimination determined for the two phenyl-substituted 'onium compounds has been compared with that reported previously for structurally related aliphatic analogues.The "anomalously" low propensity for syn-elimination as well as the "anomalously" high values of trans/cis-olefin rations in anti-elimination stigmatizing the presence of phenyl substituents are proposed to originate from a lack of base-approach hindrance in the reaction.

Cp2TiCl2-CATALYZED GRIGNARD EXCHANGE REACTIONS WITH ACETYLENES. A CONVENIENT METHOD FOR PREPARATION OF E-ALKENYL GRIGNARD REAGENTS

Disubstituted acetylenes react with isobutylmagnesium halide in the presence of a catalytic amount of Cp2TiCl2 in ether to afford E-alkenyl Grignard reagents selectively and in almost quantitative yields.The regiochemistry of this hydromagnesation reaction is high for alkylarylacetylenes and silylacetylenes giving E-ArC(MgBr)=CHR from alkylarylacetylenes, E-ArC(MgBr)=CH(SiMe3) from arylsilylacetylenes, and E-CHR=C(MgBr)(SiMe3) from alkylsilylacetylenes, respectively.Thanks to the high reactivity of the Grignard reagent, the present reaction offers a novel, selective and operationally simple route for preparation of trisubstituted olefins.

Hydrometalation. 5. Hydroalumination of Alkenes and Alkynes with Complex Metal Hydrides of Aluminium in the Presence of Cp2TiCl2

Terminal alkenes and internal alkynes are reduced rapidly and in high yield by reaction with LiAlH4, NaAlH4, LiAlMe3H, NaAlMe3H, LiAlH2(NR2)2, NaAlH2(NR2)2, or Vitride in the presence of catalytic amount of Cp2TiCl2 in THF at room temperature.When these reactions were quenched with D2O or I2, quantitative yields of the corresponding deuterium or iodine compounds were obtained in most cases.This method provides a convenient and high-yield route to alkyl- and vinylaluminium compounds as intermediates in organic synthesis.