150935-02-7

Upstream product

• 23852-76-8 2-(4-Methoxyphenyl)-2-propyl 4-nitrobenzoate 
• 121-98-2 methyl 4-methoxybenzoate 
• 4132-48-3 1-methoxy-4-(1-methylethyl)benzene 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 1098072-77-5 5-[1-(4-methoxyphenyl)-1-methylethyl]-2,2-dimethyl-1,3-dioxane-4,6-dione 
• 7428-99-1 2-(4-methoxyphenyl)propan-2-ol 
• 22666-71-3 4-methoxycumyl cation 
• 100-06-1 1-(4-methoxyphenyl)ethanone 

Relevant academic research and scientific papers

Mangana(iii/iv)electro-catalyzed C(sp3)-H azidation

Manganaelectro-catalyzed azidation of otherwise inert C(sp3)-H bonds was accomplished using most user-friendly sodium azide as the nitrogen-source. The operationally simple, resource-economic C-H azidation strategy was characterized by mild reaction conditions, no directing group, traceless electrons as the sole redox-reagent, Earth-abundant manganese as the catalyst, high functional-group compatibility and high chemoselectivity, setting the stage for late-stage azidation of bioactive compounds. Detailed mechanistic studies by experiment, spectrophotometry and cyclic voltammetry provided strong support for metal-catalyzed aliphatic radical formation, along with subsequent azidyl radical transfer within a manganese(iii/iv) manifold.

Manganese-Catalyzed Oxidative Azidation of C(sp3)-H Bonds under Electrophotocatalytic Conditions

The selective installation of azide groups into C(sp3)-H bonds is a priority research topic in organic synthesis, particularly in pharmaceutical discovery and late-stage diversification. Herein, we demonstrate a generalized manganese-catalyzed oxidative azidation methodology of C(sp3)-H bonds using nucleophilic NaN3 as an azide source under electrophotocatalytic conditions. This approach allows us to perform the reaction without the necessity of adding an excess of the substrate and successfully avoiding the use of stoichiometric chemical oxidants such as iodine(III) reagent or NFSI. A series of tertiary and secondary benzylic C(sp3)-H, aliphatic C(sp3)-H, and drug-molecule-based C(sp3)-H bonds in substrates are well tolerated under our protocol. The simultaneous gram-scale synthesis and the ease of transformation of azide to amine collectively advocate for the potential application in the preparative synthesis. Good reactivity of the tertiary benzylic C(sp3)-H bond and selectivity of the tertiary aliphatic C(sp3)-H bond in substrates to incorporate nitrogen-based functionality at the tertiary alkyl group also provide opportunities to manipulate numerous potential medicinal candidates. We anticipate our synthetic protocol, consisting of metal catalysis, electrochemistry, and photochemistry, would provide a new sustainable option to execute challenging organic synthetic transformations.

Catalytic Direct-Type Addition Reactions of Alkylarenes with Imines and Alkenes

Catalytic addition reactions of very weakly acidic nonactivated alkylarenes such as toluene and its derivatives were developed by using a strongly basic mixed catalyst system under mild reaction conditions. The addition reactions with imines and alkenes proceeded smoothly under proton-transfer conditions to afford the desired products in good to high yields, and high levels of regio- and stereoselectivity were achieved. It was also revealed that the asymmetric addition reaction of an alkylarene was possible.

Carbon-based leaving group in substitution reactions: Functionalization of sp3-hybridized quaternary and tertiary benzylic carbon centers

Lewis acid promoted substitution reactions employing Meldrum's acid and 5-methyl Meldrum's acid as carbon-based leaving groups are described which transform unstrained quaternary and tertiary benzylic Csp 3-Csp3 bonds into Csp3-X bonds (X = C, H, N). Importantly, this reaction has a broad scope in terms of both suitable substrates and nucleophiles with good to excellent yields obtained (typically >90%).

Steroid derivatives for the treatment of prostatic hypertrophy their preparation and uses

The invention includes compounds of formula (I): STR1 in which R1 is hydrogen, alkyl, aryl-substituted alkyl or aromatic heterocyclic-substituted alkyl; R2 is aryl-substituted alkyl, aromatic heterocyclic-substituted alkyl or diarylamino; and R3 is carboxy or a group of formula --CONHSO2 R4 wherein R4 is alkyl; and pharmaceutically acceptable salts and esters of the compounds. The compounds have valuable 5α-reductase inhibitory activity and can thus be used for the treatment and prophylaxis of, inter alia, prostatic hypertrophy as well as other disorders arising from excess levels of 5α-dihydro-testosterone.

The Effects of α-Substituents on the Kinetic and Thermodynamic Stability of 4-Methoxybenzyl Carbocations: Carbocation Lifetimes That Are Independent of Their Thermodynamic Stability

The following new rate constants for reaction of α-substituted 4-methoxybenzyl carbocations, 4-MeOC6H4CR1(R2)(1+), with a solvent of 50:50 (v/v) trifluoroethanol/water at 25 deg C and ionic strength 0.50 (NaClO4) are reported: 4-MeOC6H4CH(OMe)(1+), Ks = 2.2E7 s-1; 4-MeOC6H4CH(N3)(1+), ks = 3.3E5 s-1; 4-MeOC6H4C(CH3)2(1+), ks = 1.3E7 s-1; 4-MeOC6H4CH(CO2Et)(1+), ks = 1.4E7 s-1; 4-MeOC6H4CCH3(CF3)(1+), ks = 2.5E7 s-1.The values of ks for reaction of 4-MeOC6H4CR1(R2)(1+) with 50:50 (v/v) trifluoroethanol/water are nearly independent of very large changes in the thermodynamic stability of these carbocations caused by the addition of a wide range of electron-withdrawing or electron-donating groups at the α-position.In the most extreme case, the change from an α-methoxy to two α-(trifluoromethyl) substituents leads to a 23 kcal/mol thermodynamic destabilization of 4-MeOC6H4CR1(R2)(1+) relative to the neutral azide ion adducts but a 5-fold decrease in its reactivity toward solvent.The data show that the effects of α-substituents on the kinetic stability of 4-MeOC6H4CR1(R2)(1+) are complex and do not parallel the thermodynamic stability of these carbocations.The results are explained by consideration of the polar and resonance effects of the α-substituents on both the thermodynamic driving force and the intrinsic barrier for capture of the carbocations by solvent.These reactions are a new example of the consequences of the "principle of nonperfect synchronization".