1075-74-7

Usage

Synthesis Reference(s)

Tetrahedron Letters, 24, p. 5745, 1983 DOI: 10.1016/S0040-4039(00)94190-X

InChI:InChI=1/C11H14/c1-2-3-5-8-11-9-6-4-7-10-11/h2,4,6-7,9-10H,1,3,5,8H2

Upstream product

• 103-63-9 1-phenyl-2-bromoethane 
• 106-95-6 allyl bromide 
• 100-42-5 styrene 
• 2622-05-1 allylmagnesium bromide 
• 74-85-1 ethene 
• 2687-12-9 cinnamyl chloride 
• 67-56-1 methanol 
• 141543-31-9 (2-Benzyl-cyclopropylmethyl)-dimethyl-phenyl-silane 
• 17376-04-4 2-phenethyl iodide 
• 15733-63-8 5-chloropentylbenzene 
• 74940-33-3 Dithiocarbonic acid S-methyl ester S-(1-phenethyl-allyl) ester 
• 3277-89-2 phenethylmagnesium bromide 
• 107-18-6 allyl alcohol 
• 189251-09-0 1,1-Bis-(dimethyl-phenyl-silanyl)-5-phenyl-pentan-1-ol 

Downstream Products

• 86088-36-0 2-(3-phenyl-propyl)-oxirane 
• 75553-23-0 (E)-5-phenyl-2-penten-1-ol 
• 10521-91-2 5-phenylpentan-1-ol 
• 37904-38-4 5-phenylpent-1-en-3-ol 
• 66377-63-7 (1,2,3,4-tetrahydronaphthalen-4-yl)methanol 
• 154011-19-5 1,8-diphenyl-4-octene 
• 1718-50-9 1,5-diphenylpentane 
• 38899-49-9 monobenzyl-1,2,3,4-tetrahydronaphthalene 
• 87945-98-0 1,2-dibromo-5-phenylpentane 
• 117408-87-4 1-Iodomethyl-1,2,3,4-tetrahydro-naphthalene 
• 100-42-5 styrene 
• 187737-37-7 propene 
• 74-85-1 ethene 
• 106-99-0 buta-1,3-diene 

Relevant academic research and scientific papers

Cu-Catalyzed Reductive gem-Difunctionalization of Terminal Alkynes via Hydrosilylation/Hydroamination Cascade: Concise Synthesis of α-Aminosilanes

A copper-catalyzed reductive gem-difunctionalization of terminal alkynes with hydrosilanes and hydroxylamines has been developed. The reaction proceeds via hydrosilylation/hydroamination cascade, and the readily available and simple terminal alkynes can be transformed into the corresponding α-aminosilanes of medicinal interest in a single operation. Additionally, the use of chiral bisphosphine ligand successfully makes the reaction enantioselective to deliver the optically active α-aminosilanes with good enantiomeric ratios.

Strategies for protodesilylation of C-2 trialkylsilyl terminal alkenes

The mild and high yielding protodesilylation of C-2 trialkylsilyl terminal alkenes can be effected via a hydroboration-Peterson elimination protocol or, in the case of the phenyldimethylsilyl analogues, a one pot procedure using t-BuOK-18-C-6-TBAF can be used. The Royal Society of Chemistry 2000.

Hydroalkylation of Alkynes: Functionalization of the Alkenyl Copper Intermediate through Single Electron Transfer Chemistry

We have developed a method for the stereoselective coupling of terminal alkynes and α-bromo carbonyls to generate functionalized E-alkenes. The coupling is accomplished by merging the closed-shell hydrocupration of alkynes with the open-shell single electron transfer (SET) chemistry of the resulting alkenyl copper intermediate. We demonstrate that the reaction is compatible with various functional groups and can be performed in the presence of aryl bromides, alkyl chlorides, alkyl bromides, esters, nitriles, amides, and a wide range of nitrogen-containing heterocyclic compounds. Mechanistic studies provide evidence for SET oxidation of the alkenyl copper intermediate by an α-bromo ester as the key step that enables the cross coupling.

Palladium-catalyzed tandem isomerization/hydrothiolation of allylarenes

Herein we report a tandem olefin migration/hydrothiolation of allyl benzenes facilitated by an in situ generated palladium hydride. A catalyst system composed of palladium acetate and bidentate ligand dtbpx (1,2-bis(di-tert-butylphosphinomethyl)benzene in the presence of catalytic amounts of triflic acid led to the tandem transformation, which furnished benzylic thioethers. The reaction exhibits high regioselectivity and can be conducted under mild conditions. The robustness of the catalyst is displayed through reactions with coordinating thiols.

Gas-Phase Elimination Kinetics of ω-Phenylalkyl Chlorides. Participation of the Phenyl Ring

The kinetics of the gas-phase dehydrochlorination of several phenylalkyl chlorides were determined in a static system, seasoned with allyl bromide, and in the presence of the free radical inhibitor propene.The working temperature and pressure ranges were 398.8-480.6 deg C and 66-202 torr, respectively.The reactions are homogeneous, unimolecular, and follow a first-order rate law.The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for 3-chloro-1-phenylpropane, log k1 (s-1) = (13.99 +/- 0.26) - (238.4 +/- 3.5) kJ*mol-1; for 4-chloro-1-phenylbutane, log k1 (s-1) = (13.07 +/- 0.43) - (220.5 +/- 5.8) kJ*mol-1 (2.303RT)-1; and for 5-chloro-1-phenylpentane, log k1 (s-1) = (13.75 +/- 0.36) - (231.2 +/- 4.9) kJ*mol-1 (2.303RT)-1.When the rates of HCl elimination among each of the phenylalkyl chlorides are compared with those for the coresponding unsubstituted alkyl chloride, participation of the C6H5 group at the 3 position is more favored, while that at the 5 and 6 positions is rather weak.Participation of C6H5 group at the 4 position is apparently absent.

A palladium-catalyzed methylenation of olefins using halomethylboronate reagents

Methylenation of electron-rich olefins is a highly challenging reaction, for which we have developed a new methodology exploiting Pd-catalysis and halomethylboronate reagents, the latter replacing diazomethane and zinc carbenoids as methylene donors. Optimization of the reaction for norbornene and extension to several other olefins are reported, with reasonable-to-excellent yields of cyclopropanes in combination with β-H elimination products. Several mechanisms are plausible for this methylenation reaction.

Photochemistry of 5-phenyl-1-pentene in the gas phase

The photochemistry of the title compound has been studied in the gas phase using 254-nm irradiation. In addition to meta cycloadducts analogous to those observed in solution, population of S1vib in the gas phase gives several products, the relative amounts of which depend on quencher gas pressure but not on excitation wavelength. For example, in the absence of butane, the major photoproduct is compound 5. This product is formed by a [1,5] hydrogen shift in the primary photoproduct, compound 4. Compound 4 is an intramolecular meta cycloadduct that is generated in the gas phase with sufficient excess vibrational energy to undergo rearrangement unless quencher gas is present. Likewise, there is evidence that two other meta cycloadducts (2 and 3) are also formed with appreciable vibrational energy in the absence of a quencher gas. A unique intramolecular ortho cycloadduct is also formed from 1 but only within a narrow range of quencher gas pressures. This is a two-photon product, with the initial cycloadduct (11) ring opening to a cyclooctatriene (12) that photochemically closes to 6. The pressure dependence of this ortho cycloaddition may be due to a requirement for vibrational deactivation of 11 (Scheme 5) or a precursor species (Scheme 6). The overall chemistry is outlined in Scheme 7.

Synergistic Hydrocobaltation and Borylcobaltation Enable Regioselective Migratory Triborylation of Unactivated Alkenes

The structural diversity of sp3-triorganometallic reagents enhances their potentiality in the modular construction of molecular complexity in chemical synthesis. Despite significant achievements on the preparation of sp3 1,1,1- and 1,1,2-triorganometallic B,B,B-reagents, catalytic approaches that enable the installation of multiple boryl groups at skipped carbons of unactivated alkenes still remain elusive. Herein, we report a cobalt-catalyzed selective triborylation reaction of unactivated alkenes to access synthetically versatile 1,1,3-triborylalkanes. This triborylation protocol provides a general platform for regioselective trifunctionalization of unactivated alkenes, and its utility is highlighted by the synthesis of various value-added chemicals from readily accessible unactivated alkenes. Mechanistic studies, including deuterium-labelling experiments and evaluation of potential reactive intermediates, provide insight into the experimentally observed chemo- and regioselectivity.

Visible Light/Tertiary Amine Promoted Synergistic Hydroxydifluoroacetamidation of Unactivated Alkenes under Air

An efficient and novel method for regioselective hydroxydifluoroacetamidation of alkenes with bromodifluoroacetamides has been achieved via a tandem radical pathway mediated by photoredox catalysis under metal-free conditions. This transformation proceeded smoothly in the presence of Rhodamine 6G, affording a series of α,α-difluoro-γ-hydroxyacetamides in moderate to excellent yields. The significant advantages of this protocol are the low-cost photocatalyst, readily available starting materials, synthetic convenience, and wide functional group compatibility.

Access to Trisubstituted Fluoroalkenes by Ruthenium-Catalyzed Cross-Metathesis

Although the olefin metathesis reaction is a well-known and powerful strategy to get alkenes, this reaction remained highly challenging with fluororalkenes, especially the Cross-Metathesis (CM) process. Our thought was to find an easy accessible, convenient, reactive and post-functionalizable source of fluoroalkene, that we found as the methyl 2-fluoroacrylate. We reported herein the efficient ruthenium-catalyzed CM reaction of various terminal and internal alkenes with methyl 2-fluoroacrylate giving access, for the first time, to trisubstituted fluoroalkenes stereoselectively. Unprecedent TON for CM involving fluoroalkene, up to 175, have been obtained and the reaction proved to be tolerant and effective with a large range of olefin partners giving fair to high yields in metathesis products. (Figure presented.).