4885-07-8

Upstream product

• 689-97-4 3-buten-1-yne 
• 100-51-6 benzyl alcohol 
• 3355-28-0 1-Bromo-2-butyne 
• 764-01-2 methyl propargyl alcohol 
• 100-44-7 benzyl chloride 
• 100-39-0 benzyl bromide 
• 4039-82-1 Benzyl propargyl ether 
• 5633-34-1 (benzoylmethylene)dimethylsulfurane 
• 10323-20-3 D-Arabinose 
• 135697-04-0 (((4-bromobut-2-yn-1-yl)oxy)methyl)benzene 

Downstream Products

• 791845-45-9 (Z)-4,4,5,5-tetramethyl-2-(1-methyl-3-phenylmethoxy-1-propenyl)-1,3,2-dioxaborolane 
• 1379681-11-4 C₁₇H₂₅BO₃ 
• 1372206-08-0 (E)-(((3-(allyloxy)but-2-en-1-yl)oxy)methyl)benzene 
• 70388-33-9 4-benzyloxybut-1-ene 
• 27299-31-6 (Z)-((but-2-en-1-yloxy)methyl)benzene 
• 27299-30-5 (E)-((but-2-en-1-yloxy)methyl)benzene 
• 1533453-04-1 3-((benzyloxy)methyl)-1-phenylpent-4-en-1-one 

Relevant academic research and scientific papers

A Chan-Evans-Lam approach to trisubstituted vinyl ethers

Trisubstituted vinyl ethers were accessedviaChan-Evans-Lam coupling of vinyl trifluoroborates and primary aliphatic alcohols. This approach complements prior methods that required the use of neat liquid alcohol coupling partners. A palladium-catalyzed redox-relay Heck reaction was used to convert several vinyl ethers into aldehyde-functionalized 1,3-dihydroisobenzofurans.

Ligand-Enabled, Copper-Catalyzed Regio- and Stereoselective Synthesis of Trialkylsubstituted Alkenylboronates from Unactivated Internal Alkynes

We report the first copper-catalyzed regio- and stereoselective borylalkylation of dialkylsubstituted internal alkynes with bis(pinacolato)diboron and alkyl halides. A catalytically generated borylcopper species containing a novel π-accepting N-heterocycl

Palladium-catalyzed methylation of alkynyl C(sp)-H bonds with dimethyl sulfonium ylides

A novel palladium-catalyzed methylation protocol for the synthesis of methyl-functionalized internal alkynes has been established. This methylation method is achieved through a C(sp)-C(sp3) bond formation process and represents a new synthetic application of sulfonium ylides.

Copper-catalyzed highly regio- and stereoselective directed hydroboration of unsymmetrical internal alkynes: Controlling regioselectivity by choice of catalytic species

A highly selective synthesis of the αand β products by copper-catalyzed hydroboration utilizing two different catalytic copper species generated from pinacolborane (HBpin) and B2pin2 is reported. Regioselectivity in the crude reaction mixtures is found to be high, and the corresponding a products were isolated in good yields. In the case of an alkyne containing an alkenyl moiety, the regioselectivity decreased to 72:28. In hydroboration reactions catalyzed by other transition metals, selecting between hydrometalation and boryl metalation is difficult because the oxidative addition of HB to a metal center provides an H-M-B species, containing both H-M and B-M bonds. The α and β products are valuable intermediates used in the Suzuki-Miyaura cross-coupling reaction to regioselectively prepare various trisubstituted alkenes of types 5α and 5β.

Indium-mediated allenylation of aldehydes and its application in carbohydrate chemistry: Efficient synthesis of D -ribulose and 1-deoxy- D -ribulose

A two-step reaction sequence starting with the indium-mediated allenylation of aldehydes with 4-bromo-2-butyn-1-ols and subsequent ozonolysis of the resulting allenylic product was developed to generate a variety of dihydroxyacetone derivatives. The regioselectivity of the indium-promoted C-C bond-forming reaction can be manipulated through hydroxy protecting groups on 4-bromo-2-butyn-1-ol, yielding either allenes or alkynes as preferred products. Compared to established protocols, the necessary amount of indium for this type of allenylation can be decreased by a factor of two to four. The versatility of this strategy was demonstrated in thestereoselective and straightforward synthesis of D-ribulose and 1-deoxy-D-ribulose. Copyright

Palladium-Catalyzed Carbonylative Annulation of Internal Alkynes: Synthesis of 3,4-Disubstituted Coumarins

The palladium-catalyzed annulation of internal alkynes by o-iodophenols in the presence of CO results in exclusive formation of coumarins. No isomeric chromones have been observed. The best reaction conditions utilize the 2-iodophenol, 5 equiv of alkyne, 1 atm of CO, 5 mol% Pd(OAc)2, 2 equiv of pyridine, and 1 equiv of n-Bu4NCl in DMF at 120°C. The use of a sterically unhindered pyridine base is essential to achieve high yields. A wide variety of 3,4-disubstituted coumarins containing alkyl, aryl, silyl, alkoxy, acyl, and ester groups have been prepared in moderate to good yields. Mixtures of regioisomers have been obtained when unsymmetrical alkynes are employed. 2-Iodophenols with electron-withdrawing and electron-donating substituents and 3-iodo-2-pyridone are effective in this annulation process. The reaction is believed to proceed via (1) oxidative addition of the 2-iodophenol to Pd(0), (2) insertion of the alkyne triple bond into the aryl-palladium bond, (3) CO insertion into the resulting vinylic carbon-palladium bond, and (4) nucleophilic attack of the phenolic oxygen on the carbonyl carbon of the acylpalladium complex with simultaneous regeneration of the Pd(0) catalyst. This annulation process is the first example of intermolecular insertion of an alkyne occurring in preference to CO insertion.