33501-90-5

Upstream product

• 2979-70-6 2-methyl-5-phenyl-2-pentanol 
• 78-82-0 Isobutyronitrile 
• 4830-97-1 1,1-dimethyl-4-phenylbutyl chloride 
• 870-63-3 prenyl bromide 
• 6921-34-2 benzylmagnesium chloride 
• 7484-37-9 (3-phenylpropyl)triphenylphosphonium bromide 
• 67-64-1 acetone 
• 591-50-4 iodobenzene 
• 2270-59-9 1-bromo-4-methylpent-3-ene 
• 104-53-0 3-phenyl-propionaldehyde 
• 24470-78-8 isopropyltriphenylphosphonium iodide 
• 1589-82-8 phenylmagnesium bromide 
• 40463-08-9 2,2-dimethyl-3-(2-phenylethyl)oxirane 
• 108-86-1 bromobenzene 

Downstream Products

• 68426-07-3 (+/-)-1-phenyl-5-methylpentan-3-ol 
• 123718-22-9 (+/-)-2-methyl-5-phenylpent-1-en-3-ol 
• 39520-70-2 1,1-Dimethyl-2-phenyl-tetralin 
• 130409-92-6 3-fluoro-2-methyl-5-phenyl-1-pentene 
• 40463-08-9 2,2-dimethyl-3-(2-phenylethyl)oxirane 
• 104-53-0 3-phenyl-propionaldehyde 
• 67-64-1 acetone 
• 37904-41-9 2-(2,2-dimethylcyclopropyl)-1-phenylethane 
• 34586-03-3 2-methyl-5-phenylpentan-2-yl hydroperoxide 
• 4830-97-1 1,1-dimethyl-4-phenylbutyl chloride 

Relevant academic research and scientific papers

A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes

A retrosynthetic disconnection-reconnection analysis of epoxypolyenes - substrates that can undergo cyclization to podocarpane-type tricycles - reveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross-metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (E/Z, ca. 2-3:1). The method is further generalized for the cross-metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the E-geometrical isomer).

Dirhodium(II)-Mediated Alkene Epoxidation with Iodine(III) Oxidants

Dirhodium(II) complexes and iodine(III) oxidants have found useful applications in synthetic nitrene chemistry. In this study, the combination of the dirhodium(II) complex Rh2(tpa)4 (tpa = triphenylacetate) with the iodine(III) oxidant PhI(OPiv)2 is shown to promote the epoxidation of alkenes in the presence of 2 equivalents of water. The reaction can be applied to diversely substituted alkenes and the corresponding epoxides are isolated with yields of up to 90 %. A possible mechanism involves the dirhodium(II) complex as a Lewis acid species that would tune the oxidizing character of the iodine(III) reagent.

Direct Cross-Coupling of Allylic C(sp3)?H Bonds with Aryl- and Vinylbromides by Combined Nickel and Visible-Light Catalysis

An efficient protocol for the direct allylic C(sp3)?H bond activation of unactivated tri- and tetrasubstituted alkenes and their functionalization with aryl- and vinylbromides by nickel and visible-light photocatalysis has been developed. The method allows C(sp2)?C(sp3) formation under mild reaction conditions with good functional-group tolerance and excellent regioselectivity.

Alkyldisulfanium salts: Isolable, electrophilic sulfur reagents competent for polyene cyclizations

Tools that can effect electrophilic sulfur-promoted cation-π cyclizations are generally lacking, especially using alkylsulfide-based reagents. Herein we report that combining three different 1,2-dithioethers with Cl2 and SbCl5 generates isolable alkyldisulfanium salts that can effect such reactions. These new reagents can install -SMe, -SEt, and -SCH2CH2CF3 in modest, moderate, or good yield on diverse frameworks, including polyenes that terminate with electron-deficient groups. We also show that reagents such as dimethyl(methylthio)sulfonium tetrafluoroborate (DMTSF) can accomplish similar chemistry.

Enantioselective synthesis of cyclobutenes by intermolecular [2+2] cycloaddition with non-c2 symmetric digold catalysts

The enantioselective intermolecular gold-(I)-catalyzed [2+2] cycloaddition of terminal alkynes and alkenes has been achieved using non-C2-chiral Josiphos digold(I) complexes as catalysts, by the formation of the monocationic complex. This new approach has been applied to the enantioselective total synthesis of rumphellaone A.

Chelation versus Non-Chelation Control in the Stereoselective Alkenyl sp2 C?H Bond Functionalization Reaction

A hydroxy group chelation-assisted stereospecific oxidative cross-coupling reaction between alkenes was developed under mild reaction conditions. In the presence of palladium catalyst, the alkenes tethered with hydroxy functionality can couple efficiently with electron-deficient alkenes to form the corresponding multi-substituted olefin products. The hydroxy group on the substrate could play dual roles in reaction, acting as the directing group for alkenyl C?H bond activation and controlling the stereoselectivity of the products.

Molybdenum-Catalyzed Stereospecific Deoxygenation of Epoxides to Alkenes

Mild and simple catalytic systems consisting of molybdenum(VI) dichloride dioxide [MoO2Cl2] as a catalyst and a phosphine as reductant have been developed for the stereospecific deoxygenation of epoxides to alkenes. The reactions using 1,2-bis(diphenylphosphino)ethane (dppe) and triphenylphosphine (PPh3) proceed with retention and inversion of stereochemistry, respectively. The mild reaction tolerates the presence of various functional groups and affords stereodefined substituted olefins in good yields. (Figure presented.).

Cobalt-Catalyzed Cross-Coupling of Grignards with Allylic and Vinylic Bromides: Use of Sarcosine as a Natural Ligand

Sarcosine was discovered to be an excellent ligand for cobalt-catalyzed carbon-carbon cross-coupling of Grignard reagents with allylic and vinylic bromides. The Co(II)/sarcosine catalytic system is shown to perform efficiently when phenyl and benzyl Grignards are coupled with alkenyl bromides. Notably, previously unachievable Co-catalyzed coupling of allylic bromides with Grignards to linearly coupled α-products was also realized with Co(II)/sarcosine catalyst. This method was used for efficient preparation of the key intermediate in an alternative synthesis of the antihyperglycemic drug sitagliptin.

D-Glucosamine in iron-catalysed cross-coupling reactions of Grignards with allylic and vinylic bromides: Application to the synthesis of a key sitagliptin precursor

A sustainable D-glucosamine ligand is successfully introduced into iron-catalysed C-C cross-coupling reactions for the first time. The Fe(acac)2/D-glucosamine·HCl/Et3N catalytic system was effective at 5 mol% loading in coupling reactions of Grignard reagents with organic bromides. Moderate to high efficiency was achieved with preserved stereochemistry when allyl (Csp3) or alkenyl (Csp2) bromides were coupled with phenylmagnesium (Csp2) or benzylmagnesium (Csp3) bromides. The catalytic system developed was also successfully applied for the novel and economic preparation of a Michael-acceptor-like starting material used in an alternative synthesis of the drug sitagliptin, a known blockbuster for the treatment of type II diabetes mellitus.

Stereospecific Deoxygenation of Aliphatic Epoxides to Alkenes under Rhenium Catalysis

The combination of a catalytic amount of Re2O7 and triphenyl phosphite as a reductant is effective for the deoxygenation of unactivated aliphatic epoxides to alkenes. The reaction proceeds stereospecifically with variously substituted epoxides under neutral conditions and is compatible with various functional groups. Protection and deprotection of a double bond functionality using an epoxide are shown as an example of the current rhenium-catalyzed deoxygenation protocol. The effect of reductants for the stereoselectivity has also been studied, indicating that the use of electron-deficient phosphines or phosphites is the key for the stereospecific deoxygenation. (Chemical Equation Presented).