17314-92-0

Usage

Synthesis Reference(s)

Journal of the American Chemical Society, 77, p. 1774, 1955 DOI: 10.1021/ja01612a016

Upstream product

• 6130-96-7 1,1-dichloro-3,3-dimethylbutane 
• 96-37-7 methyl-cyclopentane 
• 71-43-2 benzene 
• 100-42-5 styrene 
• 41902-42-5 tri-tert-butylcarbinol 
• 594-19-4 tert.-butyl lithium 
• 100-44-7 benzyl chloride 
• 630-19-3 pivalaldehyde 
• 507-20-0 tertiary butyl chloride 
• 90878-19-6 phenethylmagnesium chloride 
• 60-12-8 2-phenylethanol 
• 31366-07-1 3,3-dimethyl-1-phenyl-butan-1-one 
• 120-12-7 anthracene 
• 2259-30-5 tert-butylmagnesium bromide 

Downstream Products

• 137039-61-3 1,4-dineohexyl-2,3,5,6-tetraethylbenzene 
• 137039-64-6 1,4-bis(3,3-dimethylbutyl)benzene 
• 137039-63-5 1-neohexyl-4-(tert-butylacetyl)benzene 

Relevant academic research and scientific papers

Compound containing carbon-silicon bond and application thereof

The invention discloses a compound containing a carbon-silicon bond and application of the compound in construction of the carbon-carbon bond. The invention provides an application of a compound containing the carbon-silicon bond as shown in a formula I or a formula I' in a chemical reaction for constructing the carbon-carbon bond, wherein one carbon in the carbon-carbon bond is from carbon connected with silicon in the compound containing the carbon-silicon bond. According to the preparation method, the compound containing the carbon-silicon bond is used for providing a carbon free radical, and the carbon free radical can directly react with carbon provided in another molecule under a mild condition to construct the carbon-carbon bond; the preparation method is wider in substrate application range, is suitable for functional group activated C and carbon free radical substrates, and is also suitable for unactivated C-H bond substrates.

Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions

Anti-Markovnikov additions to alkenes have been a longstanding goal of catalysis, and anti-Markovnikov addition of arenes to alkenes would produce alkylarenes that are distinct from those formed by acid-catalysed processes. Existing hydroarylations are either directed or occur with low reactivity and low regioselectivity for the n-alkylarene. Herein, we report the first undirected hydroarylation of unactivated alkenes with unactivated arenes that occurs with high regioselectivity for the anti-Markovnikov product. The reaction occurs with a nickel catalyst ligated by a highly sterically hindered N-heterocyclic carbene. Catalytically relevant arene- and alkene-bound nickel complexes have been characterized, and the rate-limiting step was shown to be reductive elimination to form the C–C bond. Density functional theory calculations, combined with second-generation absolutely localized molecular orbital energy decomposition analysis, suggest that the difference in activity between catalysts containing large and small carbenes results more from stabilizing intramolecular non-covalent interactions in the secondary coordination sphere than from steric hindrance.

Cobalt-Catalyzed, N-H Imine-Directed Arene C-H Benzylation with Benzyl Phosphates

A cobalt-catalyzed ortho-C-H benzylation reaction of pivalophenone N-H imines with benzyl phosphates is reported. The reaction is promoted at room temperature by a ternary catalytic system comprising Co(acac)3, a pyridylphosphine ligand, and a Grignard reagent and tolerates a series of substituted pivalophenone imines and benzyl phosphates to afford various diarylmethane derivatives in moderate yields.

Catalytic Synthesis of “Super” Linear Alkenyl Arenes Using an Easily Prepared Rh(I) Catalyst

Linear alkyl benzenes (LAB) are global chemicals that are produced by acid-catalyzed reactions that involve the formation of carbocationic intermediates. One outcome of the acid-based catalysis is that 1-phenylalkanes cannot be produced. Herein, it is reported that [Rh(μ-OAc)(η2-C2H4)2]2 catalyzes production of 1-phenyl substituted alkene products via oxidative arene vinylation. Since C C bonds can be used for many chemical transformations, the formation of unsaturated products provides a potential advantage over current processes that produce saturated alkyl arenes. Conditions that provide up to a 10:1 linear:branched ratio have been achieved, and catalytic turnovers >1470 have been demonstrated. In addition, electron-deficient and electron-rich substituted benzenes are successfully alkylated. The Rh catalysis provides ortho:meta:para selectivity that is opposite to traditional acid-based catalysis.

Tetrahydroxydiboron-Mediated Palladium-Catalyzed Transfer Hydrogenation and Deuteriation of Alkenes and Alkynes Using Water as the Stoichiometric H or D Atom Donor

There are few examples of catalytic transfer hydrogenations of simple alkenes and alkynes that use water as a stoichiometric H or D atom donor. We have found that diboron reagents efficiently mediate the transfer of H or D atoms from water directly onto unsaturated C-C bonds using a palladium catalyst. This reaction is conducted on a broad variety of alkenes and alkynes at ambient temperature, and boric acid is the sole byproduct. Mechanistic experiments suggest that this reaction is made possible by a hydrogen atom transfer from water that generates a Pd-hydride intermediate. Importantly, complete deuterium incorporation from stoichiometric D2O has also been achieved.

The cobalt-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents: A new route to constructing quaternary carbon centers

The cross-coupling of alkyl (pseudo)halides with alkyl Grignard reagents is catalyzed efficiently by a cobalt(II) chloride-lithium iodide-1,3-diene catalytic system, which provides a new synthetic tool for constructing sp 3 carbon chains. This system is particularly useful for creating quaternary carbon centers via the use of tertiary alkyl Grignard reagents. Various functional groups including esters, amides and carbamates are well tolerated.

Platinum(II) olefin hydroarylation catalysts: Tuning selectivity for the anti-Markovnikov product

PtII complexes containing unsymmetrical (pyri-dyl)pyrrolide ligands are shown to catalyze the hydroarylation of unactivated alkenes with selectivity for the anti-Markovnikov product. Substitution on the pyrrolide portion of the ligand allows effective tuning of the selectivity to anti-Markovnikov alkylarene products, whereas substitution on the pyridyl portion can promote competitive al-kenylarene production.

Iron-catalysed alkene hydrogenation and reductive cross-coupling using a bench-stable iron(II) pre-catalyst

Operationally simple, iron-catalysed hydrogenation and reductive cross-coupling protocols have been developed using a bench-stable iron(ii) pre-catalyst. The hydrogenation of 18 alkenes (50-99%) and reductive cross-coupling of vinyl halides with aryl- and alkyl Grignard reagents (8 examples, 18-99%) is reported using 3 mol% pre-catalyst and hydrogen as stoichiometric reductant (1-50 bar).

Copper nanoparticle-catalyzed cross-coupling of alkyl halides with Grignard reagents

A cross-coupling reaction between alkyl bromides and chlorides and various Grignard reagents was carried out in the presence of commercially available copper or copper oxide nanoparticles as a catalyst and an alkyne additive. The catalytic system shows high activity, a broad scope, and good functional group tolerance.

Co-catalyzed cross-coupling of alkyl halides with tertiary alkyl Grignard reagents using a 1,3-butadiene additive

The cobalt-catalyzed cross-coupling of alkyl (pseudo)halides with alkyl Grignard reagents in the presence of 1,3-butadiene as a ligand precursor and LiI is described. Sterically congested quaternary carbon centers could be constructed by using tertiary alkyl Grignard reagents. This reaction proceeds via an ionic mechanism with inversion of stereochemistry at the reacting site of the alkyl halide and is compatible with various functional groups. The use of both 1,3-butadiene and LiI was essential for achieving high yields and high selectivities.