33599-84-7

Upstream product

• 100-42-5 styrene 
• 292638-85-8 acrylic acid methyl ester 
• 67-56-1 methanol 
• 28525-69-1 (4E)-5-phenyl-4-pentenoic acid 
• 113519-11-2 trans-6-phenyl-5-(phenylsulfonyl)-3,4,5,6-tetrahydropyran-2-one 
• 6178-52-5 4-(phenylsulfonyl)butanoic acid 
• 100-52-7 benzaldehyde 
• 21040-45-9 Cinnamyl acetate 
• 96-32-2 bromoacetic acid methyl ester 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 7555-67-1 1-phenylmethylenecyclopropane 
• 1445-45-0 Trimethyl orthoacetate 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 201230-82-2 carbon monoxide 

Downstream Products

• 244016-01-1 trans-N-phenyl-5-phenyl-4-penten-1-amine 
• 33599-88-1 (E)-6-phenylhex-5-en-2-one 
• 1201903-83-4 2-benzyl-1-(p-tolyl)pyrrolidine 
• 1266062-94-5 2-benzyl-1-(4-fluorophenyl)pyrrolidine 

Relevant academic research and scientific papers

Stereodivergent Nucleophilic Additions to Racemic β-Oxo Acid Derivatives: Fast Addition Outcompetes Stereoconvergence in the Archetypal Configurationally Unstable Electrophile

Additions of carbon nucleophiles to racemic α-stereogenic β-oxo acid derivatives that deliver enantiomerically enriched tertiary alcohols are valuable, but uncommon. This article describes stereodivergent Cu-catalyzed borylative cyclizations of racemic β-oxo acid derivatives bearing tethered pro-nucleophilic olefins to deliver highly functionalized cyclopentanols containing four contiguous stereogenic centers. The reported protocol is applicable to a range of β-oxo acid derivatives, and the diastereomeric products are readily isolable by typical chromatographic techniques. α-Stereogenic-β-keto esters are typically thought to have extreme or spontaneous configurational fragility, but mechanistic studies for this system reveal an unusual scenario wherein productive catalysis occurs on the same time scale as background substrate racemization and completely outcompetes on-cycle epimerization, even under the basic conditions of the reaction.

Vinyl Sulfonium Salts as the Radical Acceptor for Metal-Free Decarboxylative Alkenylation

Vinyl sulfonium salts typically act as an electrophilic Michael acceptor, thus initiating many tandem cyclization reactions. Herein, we disclosed the novel reactivity of vinyl sulfonium salts as a radical acceptor. Using redox-active ester as an alkyl rad

A Simple Nickel Catalyst Enabling an E-Selective Alkyne Semihydrogenation

Stereoselective alkyne semihydrogenations are attractive approaches to alkenes, which are key building blocks for synthesis. With regards to the most atom-economic reducing agent dihydrogen (H2), only few catalysts for the challenging E-selective alkyne semihydrogenation have been disclosed, each with a unique substrate scope profile. Here, we show that a commercially available nickel catalyst facilitates the E-selective alkyne semihydrogenation of a wide variety of substituted internal alkynes. This results in a simple and broadly applicable overall protocol to stereoselectively access E-alkenes employing H2, which could serve as a general method for synthesis.

Bidentate auxiliary-directed alkenyl C-H allylation: Via exo-palladacycles: Synthesis of branched 1,4-dienes

An alkenyl C-H allylation by an exo-palladacycle intermediate is demonstrated, employing unactivated (Z)-Alkenes and allyl carbonates. With the use of an 8-Aminoquinoline (AQ) derived amide as the directing group, the N,N-bidentate-chelation-Assisted C-H activation protocol proceeded under mild and oxidant-free conditions with excellent selectivity. The utility of this approach is demonstrated by the preparative scale, selective conversion of inseparable Z/E alkenes and ready removal of the amide auxiliary to provide the corresponding ester.

Remote Functionalization of α,β-Unsaturated Carbonyls by Multimetallic Sequential Catalysis

The remote functionalization of α,β-unsaturated carbonyls by an array of multimetallic sequential catalytic systems is described. The reactions are triggered by hydrometalation using [Pd-H] or [Ru-H] isomerization catalysts and driven by the formation of thermodynamically more stable 1,2-vinyl arenes. The Pd-catalyzed deconjugative isomerization was combined with a Cu-catalyzed β-borylation of the transiently generated styrenyl derivatives to deliver a range of products that would not be accessible with the use of a single catalyst. [Pd/Cu] catalytic systems were also identified for the highly enantioselective α-hydroboration and α-hydroamination of the styrenyl intermediates. Difunctionalization simultaneously at the benzylic and homobenzylic positions was achieved by combining the isomerization process with Sharpless asymmetric dihydroxylation (SAD) using [Pd/Os] or [Ru/Os] couples. Starting from a simple α,β-unsaturated ester, an isomerization/dihydroxylation/lactonization sequence gave access to a naturally occurring γ-butyrolactone in good yield, with excellent diastereo- and enantioselectivity.

Iron-Catalyzed Vinylic C?H Alkylation with Alkyl Peroxides

A variety of alkyl peresters and alkyl diacyl peroxides, which are readily accessible from carboxylic acids, are utilized as general primary, secondary, and tertiary alkylating reagents for iron-catalyzed vinylic C?H alkylation of vinyl arenes, dienes, and 1,3-enynes. This transformation affords olefinic products in up to 98 % yield with high E/Z values. A broad range of functionalities, including carboxyl, boronic acid, methoxy, ester, amino, and halides, are tolerated. This protocol provides a facile approach to some olefins that are difficult to access, and hence, offers an alternative to existing systems. The synthetic utility of this method is demonstrated by late-stage functionalization of selected natural-product derivatives.

Tridentate Directing Groups Stabilize 6-Membered Palladacycles in Catalytic Alkene Hydrofunctionalization

Removable tridentate directing groups inspired by pincer ligands have been designed to stabilize otherwise kinetically and thermodynamically disfavored 6-membered alkyl palladacycle intermediates. This family of directing groups enables regioselective remote hydrocarbofunctionalization of several synthetically useful alkene-containing substrate classes, including 4-pentenoic acids, allylic alcohols, homoallyl amines, and bis-homoallylamines, under Pd(II) catalysis. In conjunction with previous findings, we demonstrate regiodivergent hydrofunctionalization of 3-butenoic acid derivatives to afford either Markovnikov or anti-Markovnikov addition products depending on directing group choice. Preliminary mechanistic and computational data are presented to support the proposed catalytic cycle.

Catalytic olefin hydroamination with aminium radical cations: A photoredox method for direct C-N bond formation

While olefin amination with aminium radical cations is a classical method for C-N bond formation, catalytic variants that utilize simple 2° amine precursors remain largely undeveloped. Herein we report a new visible-light photoredox protocol for the intramolecular anti-Markovnikov hydroamination of aryl olefins that proceeds through catalytically generated aminium radical intermediates. Mechanistic studies are consistent with a process involving amine oxidation via electron transfer, turnover-limiting C-N bond formation, and a second electron transfer step to reduce a carbon-centered radical, rendering the overall process redox-neutral. A range of structurally diverse N-aryl heterocycles can be prepared in good to excellent yields under conditions significantly milder than those required by conventional aminium-based protocols.

Enantioselective thiourea-catalyzed intramolecular cope-type hydroamination

Catalysis of Cope-type rearrangements of bis-homoallylic hydroxylamines is demonstrated using chiral thiourea derivatives. This formal intramolecular hydroamination reaction provides access to highly enantioenriched α-substituted pyrrolidine products and represents a complementary approach to metal-catalyzed methods.

The first palladium-catalyzed 1,4-addition of terminal alkenes to acrylate esters

A novel and efficient procedure for the synthesis of δ,γ- alkenyl esters with complete E-stereochemistry by the 1,4-addition of alkenes to acrylate esters in the presence of a catalytic amount of palladium chloride has been developed. This method provides