1032509-63-9

Upstream product

• 109-87-5 Dimethoxymethane 
• 19819-98-8 2-o-tolylethanol 
• 644-36-0 o-methylphenylacetic acid 
• 107-30-2 chloromethyl methyl ether 

Downstream Products

• 1338236-47-7 C₁₉H₁₈O 
• 1219468-04-8 2-(2-bromoethyl)-3-methylbenzaldehyde 
• 1219468-13-9 N-benzoylimino-3,4-dihydro-5-methylisoquinolinium betaine 

Relevant academic research and scientific papers

Enantioselective synthesis of tetrahydroisoquinoline derivatives via chiral-at-metal rhodium complex catalyzed [3+2] cycloaddition

An asymmetric [3+2] cycloaddition of C,N-cyclic azomethine imines with α,β-unsaturated 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium complex has been developed. The corresponding C-1-substituted tetrahydroisoquinoline derivatives were obtained in high yields (>90%) with excellent stereoselectivities (up to 99% ee and >20?:?1 dr). The reaction can be conducted on a gram-scale using a low catalyst loading (0.5 mol%) with high yield and selectivity.

Iridium-Catalyzed Enantioselective Hydrogenation of Oxocarbenium Ions: A Case of Ionic Hydrogenation

Ionic hydrogenation has not been extensively explored, but is advantageous for challenging substrates such as unsaturated intermediates. Reported here is an iridium-catalyzed hydrogenation of oxocarbenium ions to afford chiral isochromans with high enantioselectivities. A variety of functionalities are compatible with this catalytic system. In the presence of a catalytic amount of the Br?nsted acid HCl, an α-chloroether is generated in situ and subsequentially reduced. Kinetic studies suggest first-order kinetics in the substrate and half-order kinetics in the catalyst. A positive nonlinear effect, together with the half kinetic order, revealed a dimerization of the catalyst. Possible reaction pathways based on the monomeric iridium catalyst were proposed and DFT computational studies revealed an ionic hydrogenation pathway. Chloride abstraction and the cleavage of dihydrogen occur in the same step.

Synthesis of 5,6-Dihydropyrazolo[5,1-a]isoquinoline and Ethyl (Z)-3-Acetoxy-3-tosylpent-4-enoate through Tertiary-Amine-Catalyzed [3+2] Annulation

The 1,4-diazabicyclo[2.2.2]octane (DABCO) catalyzed divergent [3+2] annulation of C,N-cyclic azomethine imines with δ-acetoxyallenoates was developed; 5,6-dihydropyrazolo[5,1-a]isoquinolines and ethyl (Z)-3-acetoxy-3-tosylpent-4-enoates were afforded in moderate to good yields in a one-pot manner under mild conditions. This annulation reaction provides a highly efficient method to construct dinitrogen-fused heterocycles and ethyl (Z)-3-acetoxy-3-tosylpent-4-enoates at the same time.

Phosphane-Catalyzed [3+3] Annulation of C,N-Cyclic Azomethine Imines with Ynones: A Practical Method for Tricyclic Dinitrogen-Fused Heterocycles

A phosphane-catalyzed [3+3] annulation of azomethine imines with ynones has been developed. Under mild reaction conditions, the reaction proceeds smoothly to afford tricyclic dinitrogen-fused heterocyclic compounds in moderate to excellent yields with moderate to excellent stereoselectivies. Using a chiral phosphine as the catalyst, the reaction could work to give the cycloadduct in moderate yield with moderate enantioselectivity. (Figure presented.) .

A Phosphine-Catalyzed Novel Asymmetric [3+2] Cycloaddition of C,N-Cyclic Azomethine Imines with δ-Substituted Allenoates

Catalytic asymmetric [3+2] cycloadditions of C,N-cyclic azomethine imines with δ-substituted allenoates have been developed in the presence of (S)-Me-f-KetalPhos, affording functionalized tetrahydroquinoline frameworks in good yields with high diastereo- and good enantioselectivities under mild condition. The substrate scope has been also examined. This is the first time that δ-substituted allenoates have been applied as a δ,γ-C-C bond participated C 2 synthon in asymmetric synthesis. Another round: Catalytic asymmetric [3+2] cycloaddition of C,N-cyclic azomethine imines with δ-substituted allenoates have been developed in the presence of (S)-Me-f-KetalPhos, affording functionalized tetrahydroquinoline frameworks in good yields with high diastereo- and good enantioselectivities under mild conditions. This is the first example applying δ-substituted allenoates as C 2 synthons in asymmetric δ,γ-C-C bond formation.

Copper-catalyzed enantioselective additions to oxocarbenium ions: Alkynylation of isochroman acetals

We have developed an enantioselective, copper(I)-catalyzed addition of terminal alkynes to racemic isochroman acetals. This method is one of the first transition-metal-catalyzed approaches to enantioselective additions to prochiral oxocarbenium ions. In this reaction, TMSOTf is used to form the oxocarbenium ion in situ under conditions compatible with simultaneous formation of the chiral copper acetylide. By using a bis(oxazoline) ligand, good yields and enantioselectivities are observed for a variety of enantioenriched 1-alkynyl isochromans.

Enantioselective thiourea-catalyzed additions to oxocarbenium ions

Asymmetric, catalytic reactions of oxocarbenium ions are reported. Simple, chiral urea and thiourea derivatives are shown to catalyze the enantioselective substitution of silyl ketene acetals onto 1-chloroisochromans. A mechanism involving anion binding by the chiral catalyst to generate a reactive oxocarbenium ion is invoked. Catalysts bearing tertiary benzylic amide groups afforded highest enantioselectivities, with the optimal structure being derived from enantioenriched 2-arylpyrrolidine derivatives. Copyright