887572-51-2

Upstream product

• 2949-26-0 2-ethynylnaphthalene 
• 79-22-1 methyl chloroformate 
• 74-88-4 methyl iodide 
• 612-55-5 2-iodonaphthalene 
• 922-67-8 propynoic acid methyl ester 
• 218902-65-9 2-(2,2-dibromo-vinyl)-naphthalene 
• 158053-33-9 methyl 3-naphthalen-2-yl-3-oxopropanoate 

Relevant academic research and scientific papers

Organocatalytic trans Phosphinoboration of Internal Alkynes

We report the first trans phosphinoboration of internal alkynes. With an organophosphine catalyst, alkynoate esters and the phosphinoboronate Ph2P-Bpin are efficiently converted into the corresponding trans-α-phosphino-β-boryl acrylate products in moderate to good yield with high regio- and Z-selectivity. This reaction operates under mild conditions and demonstrates good atom economy, requiring only a modest excess of the phosphinoboronate. X-ray crystallography experiments allowed structural assignment of the unprecedented and densely functionalized (Z)-α-phosphino-β-boryl acrylate products.

Alkynylboration Reaction Leading to Boron-Containing π-Extended cis-Stilbenes as a Highly Tunable Fluorophore

An unprecedented boron-containing fluorophore, π-extended cis-stilbene, obtained via alkynylboration reaction of alkynamide is reported. Boron-containing π-extended cis-stilbenes emit fluorescence with high quantum yields in the solid state and exhibit aggregation-induced emission enhancement. The broad substrate scope of the alkynylboration reaction offers facile access to electronically diverse structures, enabling fine-tuning of light absorption/emission characteristics. The boron-containing π-extended cis-stilbene with a diphenylamino group displays solvatofluorochromism via an intramolecular charge-transfer transition.

Rhodium(III)-Catalyzed Redox-Neutral Cascade [3 + 2] Annulation of N-Phenoxyacetamides with Propiolates via C-H Functionalization/Isomerization/Lactonization

A Rh(III)-catalyzed cascade [3 + 2] annulation of N-phenoxyacetamides with propiolates under mild conditions using the internal oxidative O-N bond as the directing group has been achieved. This catalytic system provides a regio- and stereoselective access to benzofuran-2(3H)-ones bearing exocyclic enamino motifs with exclusive Z configuration selectivity, acceptable to good yields and good functional group compatibility. Mechanistic investigations by experimental and density functional theory studies suggest that a consecutive process of C-H functionalization/isomerization/lactonization is likely to be involved in the reaction.

Transition Metal-Free Trans Hydroboration of Alkynoic Acid Derivatives: Experimental and Theoretical Studies

We report a phosphine-catalyzed trans hydroboration of alkynoate esters and amides. The reaction proceeds under mild conditions with exclusive (E)-selectivity to afford (E)-β-boryl acrylates and (E)-β-boryl acrylamides in good to excellent yields. The reaction is tolerant of a variety of functional groups and allows efficient access to novel oxaboroles as well as a pargyline derivative (MAO inhibitor). Theoretical calculations suggest an internal hydride generates a phosphonium allenoxyborane followed by the formation of a key phosphonocyclobutene intermediate that collapses in a stereoselective, rate-limiting step.

Salt-Free Strategy for the Insertion of CO2 into C?H Bonds: Catalytic Hydroxymethylation of Alkynes

A copper(I) catalyst enables the insertion of carbon dioxide into alkyne C?H bonds by using a suitable organic base with which hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. In the presence of catalytic copper(I) chloride/4,7-diphenyl-1,10-phenanthroline, polymer-bound triphenylphosphine, and 2,2,6,6-tetramethylpiperidine as the base, terminal alkynes undergo carboxylation at 15 bar CO2 and room temperature. After filtration, the ammonium alkynecarboxylate can be hydrogenated to the primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of a salt-free overall process, in which carbon dioxide serves as a C1 building block in a C?H functionalization.

One-pot synthesis of propynoates and propynenitriles

An efficient transformation towards propynoates and propynenitriles is herein described. The practical methodology was conducted at low temperature (-78 or -60 °C) in a one-pot manner with the assistance of base rather than any transition metal catalysts. The base-induced protocol exhibits good functional group tolerance (up to 28 examples) and high efficiency (up to 92% yields) towards substituted acetylenes of great synthetic significance, which was also well demonstrated by the gram-scale reactions.

Gold(I)/Chiral N,N′-Dioxide–Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement

A highly efficient asymmetric cascade reaction between alkynyl esters and allylic alcohols has been realized. Key to success was the combination of a hydroalkoxylation reaction catalyzed by a π-acidic gold(I) complex with a Claisen rearrangement catalyzed by a chiral Lewis acidic N,N′-dioxide–nickel(II) complex. A range of acyclic α-allyl β-keto esters were synthesized in high yields (up to 99 %) with good diastereoselectivities (up to 97:3) and excellent enantioselectivities (up to 99 % ee) under mild reaction conditions. These products can be easily transformed into optically active β-hydroxy esters, β-hydroxy acids, or 1,3-diols.