81555-86-4

Upstream product

• 6738-06-3 phenylethynylmagnesium bromide 
• 75-07-0 acetaldehyde 
• 1004-22-4 (phenylethynyl)sodium 
• 925-90-6 ethylmagnesium bromide 
• 536-74-3 phenylacetylene 
• 2579-22-8 Phenylpropargyl aldehyde 
• 917-54-4 methyllithium 
• 4440-01-1 lithium phenylacetylide 
• 1817-57-8 4-phenyl-3-butyne-2-one 
• 76651-94-0 4-phenylbut-3-yn-2-yl methanesulfonate 
• 302934-10-7 (S)-1-ethyl-2-(p-tolylsulfinyl)benzene 
• 1223632-87-8 4-phenyl-2-(trimethylsilyl)but-3-yn-2-ol 
• 2028-63-9 but-3-yn-2-ol 
• 215438-84-9 methyl diphenylsulfonium triflate 

Downstream Products

• 36004-04-3 ethyl (E)-1-phenylbut-1-en-3-ol 
• 104974-60-9 rac-(Z)-4-phenylbut-3-en-2-ol 
• 1817-57-8 4-phenyl-3-butyne-2-one 
• 109431-70-1 4-phenylbut-3-yn-2-yl acetate 
• 22174-60-3 methyl 1-methyl-3-phenylprop-2-ynyl ether 
• 59409-61-9 hexa-3,4-dien-3-ylbenzene 
• 131437-38-2 (Z)-3,4-diphenylbut-3-en-2-ol 
• 74785-07-2 (Z)-4-iodo-4-phenylbut-3-en-2-ol 
• 27975-80-0 (+/-)-3-bromo-1-phenyl-1-butyne 
• 61423-03-8 (1R)-acetic acid 1-methyl-3-phenylprop-2-ynyl ester 
• 2344-70-9 1-phenyl-3-butanol 
• 35660-91-4 (Z)-1-phenylbut-2-en-1-one 
• 22965-93-1 (Z)-2-Bromo-1-phenyl-2-butyn-1-one 
• 134166-48-6 4-phenylbut-3-yn-2-amine 

Relevant academic research and scientific papers

A boron-oxygen transborylation strategy for a catalytic midland reduction

The enantioselective hydroboration of ketones is a textbook reaction requiring stoichiometric amounts of an enantioenriched borane, with the Midland reduction being a seminal example. Here, a turnover strategy for asymmetric catalysis, boron.oxygen transb

Bimetal Cooperatively Catalyzed Arylalkynylation of Alkynylsilanes

An unprecedented Pd/Rh cooperatively catalyzed arylalkynylation of alkynylsilanes was developed to merge an alkynylidene moiety with benzosilacycle. These silaarenes possess a particular aggregation-induced emission behavior. Mechanistic investigations demonstrate that the relay trimetallic transmetalation plays a pivotal role in governing this transformation.

Silver Mediated Banert Cascade with Carbon Nucleophiles

The Banert cascade of propargylic azides can be promoted by simple silver salts, and the triazafulvene intermediate can be intercepted by carbon nucleophiles. Various indoles (>25 examples, up to 92% yield) and electron-rich heterocycles were effective. T

Intercepting the Banert cascade with nucleophilic fluorine: Direct access to α-fluorinated: N H-1,2,3-triazoles

The treatment of propargylic azides with silver(i) fluoride in acetonitrile was found to yield α-fluorinated NH-1,2,3-triazoles via the Banert cascade. The reaction was regioselective and the products result from an initial [3,3] rearrangement. The reacti

An Amine-Assisted Ionic Monohydride Mechanism Enables Selective Alkyne cis-Semihydrogenation with Ethanol: From Elementary Steps to Catalysis

The selective synthesis of Z-alkenes in alkyne semihydrogenation relies on the reactivity difference of the catalysts toward the starting materials and the products. Here we report Z-selective semihydrogenation of alkynes with ethanol via a coordination-induced ionic monohydride mechanism. The EtOH-coordination-driven Cl- dissociation in a pincer Ir(III) hydridochloride complex (NCP)IrHCl (1) forms a cationic monohydride, [(NCP)IrH(EtOH)]+Cl-, that reacts selectively with alkynes over the corresponding Z-alkenes, thereby overcoming competing thermodynamically dominant alkene Z-E isomerization and overreduction. The challenge for establishing a catalytic cycle, however, lies in the alcoholysis step; the reaction of the alkyne insertion product (NCP)IrCl(vinyl) with EtOH does occur, but very slowly. Surprisingly, the alcoholysis does not proceed via direct protonolysis of the Ir-C(vinyl) bond. Instead, mechanistic data are consistent with an anion-involved alcoholysis pathway involving ionization of (NCP)IrCl(vinyl) via EtOH-for-Cl substitution and reversible protonation of Cl- ion with an Ir(III)-bound EtOH, followed by β-H elimination of the ethoxy ligand and C(vinyl)-H reductive elimination. The use of an amine is key to the monohydride mechanism by promoting the alcoholysis. The 1-amine-EtOH catalytic system exhibits an unprecedented level of substrate scope, generality, and compatibility, as demonstrated by Z-selective reduction of all alkyne classes, including challenging enynes and complex polyfunctionalized molecules. Comparison with a cationic monohydride complex bearing a noncoordinating BArF- ion elucidates the beneficial role of the Cl- ion in controlling the stereoselectivity, and comparison between 1-amine-EtOH and 1-NaOtBu-EtOH underscores the fact that this base variable, albeit in catalytic amounts, leads to different mechanisms and consequently different stereoselectivity.

An efficient nanocluster catalyst for Sonogashira reaction

Pd together with CuI has been well known as the catalyst towards Sonogashira reaction, which provides an effective route to functional alkynes. However, the achievement of high activity and selectivity of this catalytic system is still challenging in some cases. Illustrative examples include their low activity for aryl chloride substrates, and switched selectivity to oxidative coupling products in air atmosphere. In this work, a Cu-incorporated Au13 nanocluster [Au13Cu2(PPh3)6(SC2H4Ph)6]+[NO3]- (Au13Cu2) was designed and prepared in high yield via rapid synthesis. This atomically precise nanocluster shows the potential to be a novel catalytic system for Sonogashira reaction, featuring high activity and selectivity, as well as good recyclability even in air atmosphere.

Nickel-catalyzed asymmetric propargylic amination of propargylic carbonates with aniline derivatives

A study for the development of the nickel-catalyzed highly enantioselective propargylic amination of propargylic carbonates with aniline derivatives is described. The reaction of internal alkyne-substituted propargylic carbonates with a series of aniline derivatives smoothly proceeded in DMSO using a combination of Ni(cod)2 and (R)-SEGPHOS as the catalyst to give the corresponding chiral propargylic amines in 61-93% yields with 91-97% ee (24 examples).

Efficient Synthesis of Polysubstituted Furans through a Base-Promoted Oxacyclization of (Z)-2-En-4-yn-1-ols

An efficient base catalyzed oxacyclization of Z-enynols has been developed under transition metal-free reaction conditions, thus resulting in a variety of new di-, tri-, and tetra-substituted furans. This approach allowed us to obtain 32 new compounds. Furthermore, DFT calculations were realized to depict a relationship between the natural population analysis and experimental results with alkyl or aryl groups for the synthesis of 2-benzylfuran. A one-pot Sonogashira/oxacyclization approach offers a flexible, robust and efficient alternative to base catalyzed cyclization is also carried out.

Aromatic Aza-Claisen Rearrangement of Arylpropargylammonium Salts Generated in situ from Arynes and Tertiary Propargylamines

The charge-accelerated aza-Claisen rearrangement of ammonium salts serves as a key step in the construction of complex nitrogen-containing molecules. However, much less attention has been paid to the aromatic aza-Claisen rearrangement than to the aliphatic one. Herein, we report an unprecedented aromatic aza-Claisen rearrangement of arylpropargylammonium salts, generated in situ from arynes and tertiary propargylamines, delivering structurally diverse 2-propargylanilines in moderate to good yields with high regioselectivity. This rearrangement proceeds in the absence of strong bases or transition metals, is compatible with moisture and air, tolerates a wide variety of functional groups, and is amenable to forming 11- to 13-membered heterocycles with a triple bond. The 2-propargylaniline products were treated with aluminum chloride in ethanol to afford multisubstituted indoles in moderate to excellent yields. Finally, a series of deuterium-labeling experiments was performed to elucidate the reaction mechanism.

Unified Approach to Furan Natural Products via Phosphine-Palladium Catalysis

Polyalkyl furans are widespread in nature, often performing important biological roles. Despite a plethora of methods for the synthesis of tetrasubstituted furans, the construction of tetraalkyl furans remains non-trivial. The prevalence of alkyl groups in bioactive furan natural products, combined with the desirable bioactivities of tetraalkyl furans, calls for a general synthetic protocol for polyalkyl furans. This paper describes a Michael–Heck approach, using sequential phosphine-palladium catalysis, for the preparation of various polyalkyl furans from readily available precursors. The versatility of this method is illustrated by the total syntheses of nine distinct polyalkylated furan natural products belonging to different classes, namely the furanoterpenes rosefuran, sesquirosefuran, and mikanifuran; the marine natural products plakorsins A, B, and D and plakorsin D methyl ester; and the furan fatty acids 3D5 and hydromumiamicin.