83564-70-9

Upstream product

• 83564-77-6 4-methoxy-4-phenylbut-2-yn-1-ol 
• 6924-81-8 epoxy-3,4 butyne-1 
• 100-59-4 phenylmagnesium chloride 
• 23147-58-2 glycolaldehyde dimer 
• 536-74-3 phenylacetylene 
• 144425-50-3 tert-butyldimethyl((4-phenylbuta-2,3-dien-1-yl)oxy)silane 
• 100-52-7 benzaldehyde 
• 107-19-7 propargyl alcohol 
• 144425-46-7 (±) 4-(tert-butyldimethylsilyloxy)-1-phenylbut-2-yn-1-ol 
• 1334430-38-4 diethyl (phenylethynyl)boronate 

Downstream Products

• 1252575-86-2 C₁₄H₁₂S 
• 1252575-87-3 C₁₄H₁₂S 
• 1252575-89-5 C₁₆H₂₀ 
• 1252575-80-6 C₁₇H₁₆ 
• 1252575-81-7 C₁₇H₁₆ 
• 67946-07-0 (Z)-(2-vinyloct-1-en-3-(p-tolyl)-1-yl)benzene 
• 1252575-84-0 C₁₆H₁₃Br 
• 67946-11-6 1-(1-(E)-benzylidene-allyl)-4-methoxy-benzene 
• 1252575-83-9 C₁₇H₁₆O 
• 1252575-82-8 C₁₇H₁₆O 
• 1252575-85-1 C₁₈H₁₆O₂ 
• 67945-96-4 (Z)-1,3-Diphenyl-1,3-butadiene 

Relevant academic research and scientific papers

Enantio- And Diastereodivergent Construction of 1,3-Nonadjacent Stereocenters Bearing Axial and Central Chirality through Synergistic Pd/Cu Catalysis

In contrast to the widely explored methods for the asymmetric synthesis of molecules bearing a single stereocenter or adjacent stereocenters, the concurrent construction of 1,3-stereogenic centers in an enantio- and diastereoselective manner remains a challenge, especially in acyclic systems. Herein, we report an enantio- and diastereodivergent construction of 1,3-nonadjacent stereocenters bearing allenyl axial and central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic asymmetric allenylation with racemic allenylic esters. The protocol is suitable for a wide range of substrates including the challenging allenylic esters with less sterically bulky substituents and provided chiral allenylic products bearing 1,3-nonadjacent stereocenters with high levels of enantio- and diastereoselectivities (up to >20:1 dr and >99% ee). Furthermore, several representative transformations involving axial-to-central chirality transfer were conducted, affording useful structural motifs containing nonadjacent stereocenters in a diastereodivergent manner.

Highly Selective Nucleophilic 4-Aryl-2,3-allenylation of Malonates?

Allenes are a class of very important compounds and the development of straightforward, efficient, and highly enantioselective synthetic strategies for allenes have attracted extensive interests. Along this line, it is well known that aryl-substituted allenes may be readily racemized, thus, difficult to prepare in high ee. Herein, an efficient palladium-catalyzed nucleophilic allenylation of malonates with racemic 4-aryl-2,3-butadienyl carbonates has been developed. The selectivity issue of mono- vs. bis-allenylation with 2-non-substituted malonates has been addressed. By utilizing (R)-(–)-DTBM-SEGPHOS (5,5'-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4'-bi-1,3-benzodioxole) as a chiral ligand, various aryl-substituted allenes and bisallenes have been prepared with good to excellent yields with high chemoselectivity and enantioselectivity under mild reaction conditions. Au-catalyzed cycloisomerization and APK (allenic Pauson–Khand) reactions affording optically active mono- and bicyclic products have been demonstrated.

Preparation of Chiral Allenes through Pd-Catalyzed Intermolecular Hydroamination of Conjugated Enynes: Enantioselective Synthesis Enabled by Catalyst Design

In this study, we establish that conjugated enynes undergo selective 1,4-hydroamination under Pd catalysis to deliver chiral allenes with pendant allylic amines. Several primary and secondary aliphatic and aryl-substituted amines couple with a wide range of mono- and disubstituted enynes in a nonenantioselective reaction where DPEphos serves as the ligand for Pd. Benzophenone imine acts as an ammonia surrogate to afford primary amines in a two-step/one-pot process. Examination of chiral catalysts revealed a high degree of reversibility in the C-N bond formation that negatively impacted enantioselectivity. Consequently, an electron-poor ferrocenyl-PHOX ligand was developed to enable efficient and enantioselective enyne hydroamination.

Gold-catalyzed N, O-functionalizations of 6-allenyl-1-ynes with n-hydroxyanilines to construct benzo[b]-azepin-4-one cores

Gold-catalyzed reactions of 6-allen-1-ynes with N-hydroxyanilines afford thermally stable benzoazepin-4-ones in anti-selectivity; these anti-configured products are easily isomerized to their syn-isomers on a silica column. The mechanism of reactions likely involve initial nitrone/allene cycloadditions, followed by skeletal rearrangement of resulting intermediates.

Enantioselective synthesis of allenes by catalytic traceless petasis reactions

Allenes are useful functional groups in synthesis as a result of their inherent chemical properties and established reactivity patterns. One property of chemical bonding renders 1,3-substituted allenes chiral, making them attractive targets for asymmetric synthesis. While there are many enantioselective methods to synthesize chiral allenes from chiral starting materials, fewer methods exist to directly synthesize enantioenriched chiral allenes from achiral precursors. We report here an asymmetric boronate addition to sulfonyl hydrazones catalyzed by chiral biphenols to access enantioenriched allenes in a traceless Petasis reaction. The resulting Mannich product from nucleophilic addition eliminates sulfinic acid, yielding a propargylic diazene that performs an alkyne walk to afford the allene. Two enantioselective approaches have been developed; alkynyl boronates add to glycolaldehyde imine to afford allylic hydroxyl allenes, and allyl boronates add to alkynyl imines to form 1,3-alkenyl allenes. In both cases, the products are obtained in high yields and enantioselectivities.

A new protocol for nickel-catalysed regio- and stereoselective hydrocyanation of allenes

Regio- and stereoselective hydrocyanation under nickel catalysis is described. This report shows that allenyl C-C double bonds are discriminated and converted to the corresponding carbonitriles as a single product. The key functionalities for achieving high regio- and stereocontrol are aryl and cyclopropyl groups in the substrates. This journal is

A direct synthesis of allenes by a traceless petasis reaction

A one-pot synthesis of allenes by the 2-nitrobenzenesulfonylhydrazide- mediated coupling of hydroxyaldehydes or ketones with alkynyl trifluoroborate salts is reported. This mild process involves in situ formation of a sulfonylhydrazone that reacts with alkynyl trifluoroborates to generate a transient propargylic hydrazide species. Decomposition of this unstable hydrazide via an intermediate monoalkyldiazine produces the allene products through an alkene walk mechanism.

Enzymatic kinetic resolution of primary allenic alcohols. Application to the total synthesis and stereochemical assignment of striatisporolide A

Crude Porcine pancreatic lipase was successfully used for the kinetic resolution of axially chiral primary allenic alcohols providing very high enantioselectivities with E values above 200. This simple access to optically active allenes was applied to the total synthesis of the fungal metabolite (-)-striatisporolide A, allowing its unambiguous stereochemical assignment.

Selenylated dienes: synthesis, stereochemical studies by 77Se NMR, and transformation into functionalized allenes

2-Phenylselanyl-1,3-dienes 3-8 were prepared by a Wittig or Wittig-Horner-Emmons procedure starting from α-phenylselanyl α,β-unsaturated aldehydes. Ratio and configuration of each diene isomers were determined by 77Se and 1H NMR. The

A VERSATILE METHOD FOR THE PREPARATION OF ALLENIC ALCOHOLS

A convenient three step procedure to a variety of allenic alcohols is described, which relies on a highly unusual partitioning between two reaction pathways depending on the mode of addition of a reagent.