128945-83-5

Upstream product

• 49769-87-1 3-bromo-1-hexyne 
• 100-52-7 benzaldehyde 
• 18998-78-2 1-phenyl-hept-2-yn-1-one 
• 3844-94-8 1-(trimethylsilyl)-1-hexyne 
• 542-69-8 1-iodo-butane 
• 4187-87-5 1-Phenyl-2-propyn-1-ol 
• 74-96-4 ethyl bromide 
• 693-02-7 hex-1-yne 
• 766-97-2 4-n-methylphenylacetylene 
• 93-89-0 benzoic acid ethyl ester 
• 17689-03-1 1-hexynyllithium 
• 1119-67-1 1-iodo-1-hexyne 
• 218793-76-1 triethoxy(hex-1-yn-1-yl)silane 
• 875877-89-7 [(1-phenyl-2-heptynyl)oxy]-trimethylsilane 

Downstream Products

• 600163-39-1 1-phenylhept-2-yn-1-yl (1-bromo-2-methoxyprop-2-yl) ether 
• 648433-39-0 1-(dec-1-en-5-yn-4-yl)benzene 
• 1003841-32-4 C₂₀H₂₀O₂ 

Relevant academic research and scientific papers

Indium-mediated carbonyl alkynylation

Indium mediates a Barbier-type reaction between alkynyl halides and aldehydes or ketones to give secondary or tertiary propargyl alcohols. Secondary alcohols can be oxidised in situ according an Oppenauer process.

Enantioselective alkynylation of a prochiral ketone catalyzed by C2-symmetric diamino diols

C2-Symmetric diamino diols were used as chiral ligands to induce the asymmetric addition of lithium acetylides to carbonyl groups. The enantiomeric excesses (up to 99% ee) depended on the structure of the acetylene.

Au(I)-catalyzed cycloaddition pathways of non-terminal propargyl substrates

Novel chiral menthol-based pyridyl nitrone ligands were synthesized and Au(I) coordination of the ligands gave chiral Au(I)–nitrone complexes. 1H NMR studies of the gold(I) coordination experiments with nitrone ligands afforded a convenient method for monitoring complex formation. The catalytic effect of Au(I)–nitrone complexes, shown to tune catalytic systems to produce uncommon products, was evaluated in [2 + 2 + 2] cyclotrimerization and [2 + 4] cyclodimerization reactions of non-terminal propargyl acetals. Alternative gold(I)-catalyzed [2 + 2], [2 + 4] and [3 + 4] cycloaddition reaction pathways of non-terminal propargyl acetals with imine substrates gave a diverse range of N-heterocyclic products. The present screening study demonstrates the potential and the versatility of non-terminal propargyl acetals in gold(I)-catalyzed cycloaddition reactions.

Rhodium-catalyzed isomerization of α-arylpropargyl alcohols to indanones: Involvement of an unexpected reaction cascade

A rhodium-catalyzed isomerization of α-arylpropargyl alcohols to indanones has been developed under mild conditions. Considering the ease of preparation of these propargyl alcohols (terminal alkynes + aromatic aldehydes), this method provides a new way of constructing indanones with high efficiency. By the mechanistic investigations using deuterium-labeled substrates, it has also been demonstrated that the reaction goes through an unexpected cascade, with a 1,4-hydrogen shift being the turnover-limiting step of the catalytic cycle. Copyright

Efficient Synthesis of Polysubstituted Pyrroles Based on [3+2] Cycloaddition Strategy Utilizing [1,2]-Phospha-Brook Rearrangement under Br?nsted Base Catalysis

An efficient method for the synthesis of polysubstituted pyrroles was established based on the [3+2] cycloaddition strategy utilizing the [1,2]-phospha-Brook rearrangement under Br?nsted base catalysis. The less-explored approach of the [3+2] cycloaddition, that is, the reaction of a C3 subunit with imines, was successfully achieved by making use of newly designed C3 subunits containing the requisite umpolung. The two-step formal [3+2] cycloaddition involves the catalytic generation of an α-oxygenated propargyl anion through the [1,2]-phospha-Brook rearrangement followed by γ-addition to the imine under Br?nsted base catalysis and the subsequent intramolecular cyclization mediated by Au catalyst or a halogenation reagent to afford polysubstituted pyrroles having a variety of substituents in a positional selective manner. The pyrroles thus synthesized were amenable to further transformations, such as palladium-catalyzed cross-coupling reactions. The operationally very simple method with readily available substrates provides new access to a diverse array of well-organized polysubstituted pyrroles.

Iridium-catalyzed [2+2+2] cycloaddition of α,ω-diynes with alkynyl ketones and alkynyl esters

We found that the combination of [Ir(cod)Cl]2 and rac-BINAP served as an efficient catalyst for the [2+2+2] cycloaddition of 2,7-nonadiyne derivatives and related compounds with alkynyl ketones and alkynyl esters. The corresponding products wer

Rhodium-Catalyzed C?H Activation/Annulation Cascade of Aryl Oximes and Propargyl Alcohols to Isoquinoline N-Oxides

A β-hydroxy elimination instead of common oxidization to carbonyl group in secondary propargyl alcohols was successfully developed to form 2-benzyl substituted isoquinoline N-oxides by a Rhodium-catalyzed C?H activation and annulation cascade, in which moderate to excellent yields (up to 92%) could be obtained under mild reaction conditions, along with good regioselectivity, broad generality and applicability. (Figure presented.).

Straightforward Stereoselective Synthesis of Seven-Membered Oxa-Bridged Rings through in Situ Generated Cycloheptenol Derivatives

An iodine-mediated stereoselective synthesis of seven-membered oxa-bridged rings via in situ generated cycloheptenols was reported. This process was realized through the combination of C-C σ-bond cleavage and C-O bond-forming reactions in a one-pot fashion from simple and easily accessible raw materials. The formation of carbon radicals initiated by I2 was the key to the reaction.

Gold-Catalyzed Hydroamination of Propargylic Alcohols: Controlling Divergent Catalytic Reaction Pathways to Access 1,3-Amino Alcohols, 3-Hydroxyketones, or 3-Aminoketones

A versatile approach to the valorization of propargylic alcohols is reported, enabling controlled access to three different products from the same starting materials. First, a general method for the hydroamination of propargylic alcohols with anilines is described using gold catalysis to give 3-hydroxyimines with complete regioselectivity. These 3-hydroxyimines can be reduced to give 1,3-amino alcohols with high syn selectivity. Alternatively, by using a catalytic quantity of aniline, 3-hydroxyketones can be obtained in high yield directly from propargylic alcohols. Further manipulation of the reaction conditions enables the selective formation of 3-aminoketones via a rearrangement/hydroamination pathway. The utility of the new chemistry was exemplified by the one-pot synthesis of a selection of N-arylpyrrolidines and N-arylpiperidines. A mechanism for the hydroamination has been proposed on the basis of experimental studies and density functional theory calculations.

Cascade Reaction of Propargyl Amines with AgSCF3, as Well as One-Pot Reaction of Propargyl Amines, AgSCF3, and Di- tert-butyl Peroxide: Access to Allenyl Thiocyanates and Allenyl Trifluoromethylthioethers

An efficient cascade reaction of propargyl amines with AgSCF3 and KBr is developed, affording allenyl thiocyanates at room temperature in high yields. This transformation proceeds via the in situ formation of isothiocyanate intermediates, followed by a [3,3]-sigmatropic rearrangement. The resulting allenyl thiocyanates bearing 3-(electro-donating phenyl) substitutions without isolation can then be reacted with di-tert-butyl peroxide and AgSCF3 under reflux to generate novel allenyl trifluoromethylthioether compounds in moderate to good yields via a "one-pot" three-step process.