634599-51-2

Upstream product

• 107-18-6 allyl alcohol 
• 170456-80-1 3-iodo-1-tosyl-1-indole 
• 464200-92-8 (E)-methyl 3-(1-tosyl-1H-indol-3-yl)acrylate 
• 98-59-9 p-toluenesulfonyl chloride 
• 487-89-8 Indole-3-carboxaldehyde 
• 50562-79-3 1-(4-tolylsulfonyl)indole-3-carboxaldehyde 
• 151451-40-0 ethyl (E)-3-[1-(4-toluenesulfonyl)indole-3-yl]propenoate 

Downstream Products

• 1581720-38-8 (2S,3S,E)-N-benzyl-2-(dimethylamino)-3-(1-tosyl-1H-indol-3-yl)pent-4-enamide 
• 1581720-57-1 (E)-N,N-dimethyl-3-(1-tosyl-1H-indol-3-yl)prop-2-en-1-amine 
• 1581720-71-9 C₁₈H₁₆BrNO₂S 

Relevant academic research and scientific papers

Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes

Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.

Highly Enantioselective, Base-Free Synthesis of α-Quaternary Succinimides through Catalytic Asymmetric Allylic Alkylation

The synthesis of diversely substituted five-membered ring succinimide derivatives is reported featuring a direct, base-free, palladium-catalyzed asymmetric allylic alkylation. The method allows a straightforward access to the desired heterocyclic scaffold bearing an all-carbon α-quaternary stereogenic center in high yields and good to excellent enantioselectivities. To further demonstrate the synthetic utility of the method, the allylated products were further converted to various versatile chiral building blocks, including a chiral pyrrolidine and a spirocyclic derivative, using selective transformations.

Tandem Palladium and Isothiourea Relay Catalysis: Enantioselective Synthesis of α-Amino Acid Derivatives via Allylic Amination and [2,3]-Sigmatropic Rearrangement

A tandem relay catalytic protocol using both Pd and isothiourea catalysis has been developed for the enantioselective synthesis of α-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent in situ enantioselective [2,3]-sigmatropic rearrangement catalyzed by the isothiourea benzotetramisole forms syn-α-amino acid derivatives with high diastereo- and enantioselectivity. This methodology is most effective using 4-nitrophenylglycine esters and tolerates a variety of substituted cinnamic and styrenyl allylic ethyl phosphates. The use of challenging unsymmetrical N-allyl-N-methylglycine esters is also tolerated under the catalytic relay conditions without compromising stereoselectivity.

Diastereoselective Synthesis of trans-2,3-Diaryl(heteroaryl)-3,6-dihydropyrans by an Allylboration/Ring-Closing-Metathesis Sequence

trans-2,3-Diaryl(heteroaryl)-dihydropyrans were synthesized by an allylboration/ring-closing-metathesis sequence, using allylboranes formed in situ from the corresponding allylic alcohols. Aryl(heteroaryl) substituents were thus installed diastereoselectively onto dihydropyran rings in a trans fashion. These disubstituted dihydropyrans were further transformed into monosaccharide-like tetrahydropyrans.

An isothiourea-catalyzed asymmetric [2,3]-rearrangement of allylic ammonium ylides

Benzotetramisole promotes the catalytic asymmetric [2,3]-rearrangement of allylic quaternary ammonium salts (either isolated or prepared in situ from p-nitrophenyl bromoacetate and the corresponding allylic amine), generating syn-α-amino acid derivatives with excellent diastereo- and enantioselectivity (up to >95:5 dr; up to >99% ee).

Rhenium-catalyzed 1,3-isomerization of allylic alcohols: Scope and chirality transfer

(Chemical Equation Presented) The scope of the triphenylsilyl perrhennate (O3ReOSiPh3, 1) catalyzed 1,3-isomerization of allylic alcohols has been thoroughly explored. It was found to be effective for a wide variety of secondary and tertiary allylic alcohol substrates bearing aryl, alkyl, and cyano substituents. Two general reaction types were found which gave high levels of product selectivity: those driven by formation of an extended conjugated system and those driven by selective silylation of a particular isomer. The efficiency of chirality transfer with various substrates was investigated, and conditions were found in which secondary and tertiary allylic alcohols could be formed with high levels of enantioselectivity. Consideration of selectivity trends with respect to the nature of the substituents around the allylic system revealed that this is a reliable and predictable method for allylic alcohol synthesis.

The Total Synthesis of (+)-Hapalindole Q by an Organomediated Diels-Alder Reaction

The total synthesis of (+)-hapalindole Q has been achieved. The key step is a Diels-Alder reaction mediated by MacMillan's organocatalyst to provide the critical intermediate with high enantiose-lectivity (93% ee). This step establishes the proper arrange