59588-12-4

Upstream product

• 93-55-0 1-phenyl-propan-1-one 
• 80-48-8 methyl p-toluene sulfonate 
• 67-56-1 methanol 
• 698-87-3 3-phenyl-2-propanol 
• 824-47-5 (1-chloropropan-2-yl)benzene 
• 10304-81-1 1-phenyl-2-chloropropane 
• 22665-13-0 1-phenylallyl methyl ether 
• 593-53-3 Methyl fluoride 
• 1517-68-6 (S)-1-phenylpropan-2-ol 
• 23946-74-9 1-methoxypropan-2-yl 4-methylbenzenesulfonate 
• 100-58-3 phenylmagnesium bromide 
• 93-54-9 1-Phenyl-1-propanol 
• 74-88-4 methyl iodide 
• 34733-61-4 (3-bromo-1-methoxypropyl)benzene 

Downstream Products

• 103-65-1 phenylpropane 
• 29393-16-6 methyl 2-methyl-3-phenylpropionate 
• 2046-17-5 methyl 3-(benzyl)propanoate 
• 2294-71-5 methyl 2-phenylbutanoate 
• 2114-00-3 2-bromo-1-phenyl-1-propanone 
• 93-55-0 1-phenyl-propan-1-one 
• 71-43-2 benzene 

Relevant academic research and scientific papers

Formation of Cyclopropanes via Activation of (γ-Methoxy)alkyl Gold(I) Complexes with Lewis Acids

Treatment of the gold 3-methoxy-3-phenylpropyl complex (P)AuCH2CH2CH(OMe)Ph [P = P(t-Bu)2o-biphenyl] with AlCl3 at -78 °C led to the immediate (≤5 min) formation of a 4:1 mixture of phenylcyclopropane and (1-methoxypropyl)benzene in 86 ± 5% combined yield. Lewis acid activation of the stereochemically pure isotopomer erythro-(P)AuCH2CHDCH(OMe)Ph led to the formation of cis-2-deuterio-1-phenylcyclopropane in 84 ± 5% yield as a single stereoisomer, which established that cyclopropanation occurred with inversion of the γ-stereocenter. Similarly, ionization of the stereochemically pure cyclohexyl gold complex cis-(P)AuCHCH2CH(OMe)CH2CH2CH2 at -78 °C formed bicyclo[3.1.0]hexane in 82% ± 5% yield, which validated a low energy pathway for cyclopropanation involving inversion of the α-stereocenter. Taken together, these observations are consistent with a mechanism for cyclopropane formation involving backside displacement of both the Cγleaving group and the Cα (L)Au+ fragment via a W-shaped transition state.

Cyclopropyl Group: An Excited-State Aromaticity Indicator?

The cyclopropyl (cPr) group, which is a well-known probe for detecting radical character at atoms to which it is connected, is tested as an indicator for aromaticity in the first ππ* triplet and singlet excited states (T1 and S1). Baird's rule says that the π-electron counts for aromaticity and antiaromaticity in the T1 and S1 states are opposite to Hückel's rule in the ground state (S0). Our hypothesis is that the cPr group, as a result of Baird's rule, will remain closed when attached to an excited-state aromatic ring, enabling it to be used as an indicator to distinguish excited-state aromatic rings from excited-state antiaromatic and nonaromatic rings. Quantum chemical calculations and photoreactivity experiments support our hypothesis; calculated aromaticity indices reveal that openings of cPr substituents on [4n]annulenes ruin the excited-state aromaticity in energetically unfavorable processes. Yet, polycyclic compounds influenced by excited-state aromaticity (e.g., biphenylene), as well as 4nπ-electron heterocycles with two or more heteroatoms represent limitations.

Peroxometalates immobilized on magnetically recoverable catalysts for epoxidation

Magnetically separable catalysts were prepared and employed for the epoxidation of olefins with hydrogen peroxide. In all cases the magnetic core was firstly covered with a silica layer to prevent iron ion-initiated decomposition of hydrogen peroxide. The catalytic active species, an ionic liquid-type peroxotungstate, was then immobilized either by hydrogen bonding (catalyst 1) or by covalent SiO linkage (catalyst 2). In addition to a thorough characterization by FT-IR, XRD, NMR, DRIFT, XPS, and TEM, the catalytic potential was evaluated in the epoxidation of a variety of olefins as well as allylic alcohols. Both catalysts showed essentially a constant activity after at least ten consecutive cycles. On the basis of the research above, a new type of magnetically separable catalyst was constructed by immobilization of lacunary-type phosphotungstate by hydrogen bonding between the sulfonate anion and silanol group on the surface of the core-shell magnetic nanoparticles. After the detailed characterization, the catalyst was used in the epoxidation of a variety of olefins and allylic alcohols and was found to possess high activity, selectivity towards epoxides, and a constant activity after at least ten catalytic recycles without solvent.

Iron-catalyzed cross-coupling of alkyl sulfonates with arylzinc reagents

Iron-catalyzed cross-coupling reactions of primary and secondary alkyl sulfonates with arylzinc reagents proceed smoothly In the presence of excess TMEDA and a concomitant magnesium salt. The arylzinc reagents are prepared from the corresponding aryllithium or magnesium reagents with ZnI2. The In situ formation of alkyl Iodides and consecutive rapid cross-coupling avoids discrete preparation of the unstable secondary alkyl halides and also achieves high product selectivity.

Wagner-Meerwein rearrangements in the gas phase: Anchimeric assistance to acid-induced dissociation of optically active phenylpropanols

The kinetics and the stereochemistry of Wagner-Meerwein rearrangements of O-protonated and O-methylated (S)-1-phenyl-2-propanol (1s(A)+; A=H or Me) and (S)-2-phenyl-1-propanol (2S(A)+; A=H or Me) have been investigated in the gas phase at 750 Torr and in the 25-140°C temperature range. The 1S(A) and 2S(A)+ intermediates were generated in the gas phase by reaction of the C(n)H5+(n=1, 2; A= H) and (CH3)2F+ ions (A - Me), formed by stationary γ radiolysis of bulk CH4 and CH3F, respectively, with the corresponding optically active alcohols. The results are consistent with unimolecular H2O loss from both 1s(H)+ and 2s(H); this is anchimerically assisted by all the groups adjacent to the leaving moiety. Anchimeric assistance appears much less efficient in both 1S(Me)+ and 2S(Me)+. Analysis of the activation parameters indicates that competing neighboring-group participation in C-O bond fission in 1s(H)+ and 2s(H) respond essentially to entropic rather than enthalpic factors. The stereochemical distribution of the reaction products allowed us to discern between backside and frontside phenyl-group participation in 1s(H+). The counterintuitive observation of a frontside Ph participation, with an activation energy 1.3±0.5 kcal mol-1 lower than that of the accompanying backside assistance, is attributed to conformational factors and to the stabilizing electrostatic interactions between the phenonium ion and the leaving H2O complex that is spatially allowed only in the frontside participation and forbidden in the backside one.

The β-heteroatom effect on carbenes

The β-thiophosphinoyl carbene PhCCH2P(S)Ph2 (5) has been prepared by irradiation of the corresponding diazo compound. The relative rates for insertion into the OH bond of methanol and for addition to the double bond of 2-methyl-2-but

Controlling factors determining the regiochemistry of intramolecular alkoxymercuration

The intramolecular alkoxymercuration of (E)-5-arylpent-4-en-1-ols indicated that the regioselectivity is closely related to the Hammett constants of the para-substituents on the benzene ring. Large solvent effects on the regioselectivity were also observe

Photolyses of 1,4-Bis(1,1-diarylhept-2-ynyl)benzenes and 1,4-Bis(1,1-diarylalkyl)benzenes

Photolyses of 1,4-bis(1,1-diarylhept-2-ynyl)benzenes or 1,4-bis(1,1-diarylalkyl)benzenes 2 in a tetrahydrofuran-methanol mixture gave 1-biphenyl-4-yl-1,1-diarylhept-2-ynes or 1-biphenyl-4-yl-1,1-diarylalkanes 3 as major products and biaryls 1 as minor products.The products 3 were obtained with quantum yields of 0.010-0.020, respectively.

Gas-Phase Acid-Induced Nucleophilic Displacement Reactions. 7. Structural and Stereochemical Evidence for the Existence and the Relative Stability of Alkylenebenzenium Ions in the Gas Phase

A comprehensive investigation on the existence and relative stability of gaseous 2,3-butylene- and 1,2-propylenebenzenium ions was carried out by establishing the structural features and the stereochemistry of acid-induced displacement by CH3OH on isomeric 3-phenylbutyl-2 onium and β-phenylpropyl onium intermediates.The latter were obtained in the gas phase from the reaction of radiolytically formed GA+ (GA+ = D3+, CnH5+ (n=1,2), i-C3H7+, and CH3FCH3+) acids with isomeric 3-phenyl-2-chlorobutanes and β-phenyl-Y-propanes (Y = Cl, OH).The analysis of the isomeric distribution of the neutral substitution products allows the establishment of extensive phenyl-group participation in the displacement process, occuring in competition with methyl and hydrogen 1,2-transfers.The participating ability of a phenyl moiety adjacent to the substitution center is found to depend essentially upon the configuration of the precursor and to be related to its gas-phase nucleophilicity.The occurence of relatively stable cyclic alkylenebenzenium ions as static intermediates in these displacement reactions is suggested by the particular isomeric and stereoisomeric distribution of the products and by its comparison with that obtained from open-chain isomeric ions.The results obtained from the present gas-phase experiments are discussed in the light of those from related gas-phase and solution studies.

PHASE TRANSFER CATALYSIS AND HOMOGENEOUS REACTIONS WITH β-OXYALKYL RADICALS FROM ORGANOMERCURIALS

β-Alkoxy- and β-hydroxyalkyl radicals generated by sodium borohydride reduction of oxymercurials react with electron deficient olefins to give addition compounds in a homogeneous process.Heterogeneous reactions are also successful in the presence of catalytic amounts of surfactants and provide a superior method for the "one pot" reductive alkylation of oxymercurials.