105902-61-2

Upstream product

• 103-71-9 phenyl isocyanate 
• 556-82-1 3-methyl-2-buten-1-ol 
• 2603-10-3 N-phenyl methyl carbamate 

Downstream Products

• 63972-14-5 1-(dimethylphenylsilyl)-3-methyl-2-butene 
• 94286-53-0 (2-methyl-3-buten-2-yl)dimethylphenylsilane 

Relevant academic research and scientific papers

Br?nsted Base Assisted Photoredox Catalysis: Proton Coupled Electron Transfer for Remote C?C Bond Formation via Amidyl Radicals

The synthesis of alkyne- and alkene-decorated lactams has been achieved through a photoredox-initiated radical cascade reaction. The developed Br?nsted base assisted, photoredox-catalyzed, intramolecular 5-exo-trig cyclization/intermolecular radical addit

Photoredox-Catalyzed Difunctionalization of Unactivated Olefins for Synthesizing Lactam-Substituted gem-Difluoroalkenes

Herein, the synthesis of lactam-substituted gem-difluoroalkenes has been developed through a photoredox-catalyzed radical cascade reaction. This developed photoredox-catalyzed, Br?nsted base-assisted intramolecular 5-exo-trig cyclization/intermolecular radical addition/β-fluoride elimination reaction offers a simple method for producing lactam, carbamate, or urea-substituted gem-difluoroalkenes with good functional group tolerance and high yields.

Formal Aza-Wacker Cyclization by Tandem Electrochemical Oxidation and Copper Catalysis

In oxidative electrochemical organic synthesis, radical intermediates are often oxidized to cations on the way to final product formation. Herein, we describe an approach to transform electrochemically generated organic radical intermediates into neutral

Transition Metal Free Cycloamination of Prenyl Carbamates and Ureas Promoted by Aryldiazonium Salts

Upon treatment with aryldiazonium salts, prenyl carbamates and ureas undergo redox-neutral azocycloamination. In general, N-aryl O-prenyl carbamates cyclize in a photocatalytic reaction with visible light and an organic dye. With electron-deficient diazonium salts, electronic matching with an electron-rich N-aryl substituent results in a reaction proceeding in the ground state, without either light or photocatalyst. Cyclic voltammetry suggests that this radical reaction is initiated by hydrogen-atom abstraction mediated by an aryl radical, followed by a radical addition cascade and proton-coupled hole propagation. The reaction proceeds at room temperature in short reaction times, and a range of functional groups is tolerated.

An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization

Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process.

Catalytic Alkene Carboaminations Enabled by Oxidative Proton-Coupled Electron Transfer

Here we describe a dual catalyst system comprised of an iridium photocatalyst and weak phosphate base that is capable of both selectively homolyzing the N-H bonds of N-arylamides (bond dissociation free energies ～ 100 kcal/mol) via concerted proton-couple

Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer

Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

Lanthanum(III) isopropoxide catalyzed chemoselective transesterification of dimethyl carbonate and methyl carbamates

A practical transesterification of less reactive dimethyl carbonate and much less reactive methyl carbamates with primary (1°), secondary (2°), and tertiary (3°) alcohols was established with the use of a lanthanum(III) complex, which was prepared in situ from lanthanum (III) isopropoxide (3 mol %) and 2-(2-methoxyethoxy)ethanol (6 mol %). In particular, corresponding carbonates and carbamates obtained were of synthetic utility from the viewpoint of the selective protection and/or deprotection of 1°-, 2°-, and 3°-alcohols.

Practical synthesis of allylic silanes from allylic esters and carbamates by stereoselective copper-catalyzed allylic substitution reactions

The first copper-catalyzed allylic substitution reactions of allylic acetates and carbamates employing a bis(triorganosilyl)zinc reagent are reported. This novel procedure avoids the use of stoichiometric amounts of copper salts which are usually mandatory with this chemistry. Application of this methodology to standard model substrates substantiates a high diastereoselectivity for the double bond geometry (E:Z) as well as the relative configuration (syn:anti).

A Regioselective and Stereospecific Synthesis of Allylsilanes from Secondary Allylic Alcohol Derivatives

Primary and secondary allylic acetates and benzoates react with the dimethyl(phenyl)silyl-cuprate reagent to give allylsilanes, provided that the THF in which the cuprate is prepared is diluted with ether before addition of the allylic ester.The reaction is reasonably regioselective in some cases: (i) when the allylic system is more-substituted at one end than the other, as in the reactions 4->5 and 9->10; (ii) when the steric hindrance at one end is neopentyl-like, as in the reactions 15->16; and (iii) when the disubstituted double bond has the Z configuration, as in th e reactions Z-19->E-21 or, better, because the silyl group is becoming attached to the less-sterically hindered end of the allylic system, Z-20->E-22.The regioselectivity is better if a phenyl carbamate is used in place of the ester, and a three-step protocol assembling the mixed cuprate on the leaving group is used, as in the reactions 23->24 and E- or Z-29->E-21, or, best of all, because the silyl group is again becoming attached to the less-sterically hindered end of the allylic system, E- or Z-30->E-22.This sequence works well to move the silyl group onto the more substituted end of an allyl system, but only when the move is from a secondary allylic carbamate to a tertiary allylsilane, as in the reaction 38->39.Allyl(trimethyl)silanes can be made using alkyl- or aryl-cuprates on trimethylsilyl-containing allylic esters and carbamates, as in the reactions 40->41, and 43->44.The reaction of the silyl-cuprate with allylic esters and the three-step sequence with the allylic carbamates are stereochemically complementary, the former being stereospecifically anti and the latter stereospecifically syn.Homochiral allylsilanes can be ma de by these methods with high levels of stereospecificity, as shown by the synthesis of the allylsilanes 54, 58 and 59.