69511-49-5

Upstream product

• 6089-04-9 3-(tetrahydropyran-2'-yloxy)propyne 
• 79-22-1 methyl chloroformate 
• 109-72-8 n-butyllithium 
• 74-86-2 acetylene 
• 110-87-2 3,4-dihydro-2H-pyran 

Downstream Products

• 6581-66-4 2-methoxytetrahydropyran 
• 31555-05-2 methyl 4-hydroxy-2-butynoate 
• 76143-45-8 methyl 5-(α-chloro-α-cyanomethyl)-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-v-triazole-4-carboxylate 
• 76143-43-6 methyl 5-(α-cyano-α-hydroxymethyl)-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-v-triazole-4-carboxylate 
• 76143-51-6 methyl 1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-5-carboxy-v-triazole-4-carboxylate 
• 76143-39-0 methyl 5-hydroxymethyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-v-triazole-4-carboxylate 
• 76143-47-0 methyl 1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-5-chloromethyl-v-triazole-4-carboxylate 
• 76143-42-5 methyl 5-formyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-v-triazole-4-carboxylate 
• 76143-40-3 methyl 5-carbomethoxy-4-hydroxymethyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-v-triazole-4-carboxylate 
• 76143-48-1 methyl 5-methyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-v-triazole-4-carboxylate 
• 73591-52-3 Methyl 5-Cyanomethyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-1,2,3-triazole-4-carboxylate 
• 146668-87-3 C₁₆H₁₇⁽²⁾H₄BrO₃ 
• 868050-54-8 3-methoxy-2,4-dimethoxycarbonyl-5-(tetrahydropyranyloxymethyl)phenol 
• 681126-32-9 2-[[4-(4-iodophenoxy)-2-methylbut-2-enyl]oxy]tetrahydro-2H-pyran 

Relevant academic research and scientific papers

Gold-Catalyzed Bicyclic and [3+2]-Annulations of Internal Propargyl Alcohols with Nitrones and Imines To Yield to Two Distinct Heterocycles

A gold-catalyzed synthesis of 1,3-dihydrooxazolo[3,4-a]indoles from 1-oxo-3-yn-4-ols and nitrones is described; this new bicyclic annulation presents the first examples that internal alkynes can react with nitrones to undergo an oxoarylation route. DFT calculations indicate a [3,3]-sigmatropic shift of initial alkenylgold intermediates to elude the intermediacy of gold carbenes. We also developed new [3+2]-annulations of the same 1-oxo-3-yn-4-ols with imines, yielding oxazolidin-4-ylidene derivatives efficiently. The tethered alcohols of these 1-oxo-3-ynes allow trapping of their metastable 2-azadienium intermediates to enable a novel annulation. Our mechanistic analysis indicates that the two products, despite their structural relevance, are produced from two independent systems. (Figure presented.).

Catalytic (3+2) Palladium-Aminoallyl Cycloaddition with Conjugated Dienes

We describe the design and application of tailored aminoallyl precursors for catalytic (3+2) cycloaddition with conjugated dienes via a Pd-aminoallyl intermediate. The new cycloaddition reactions override the conventional (4+3) selectivity of aminoallyl cation cycloaddition through a sequence of Pd-allyl transfer and ring closure. A variety of highly substituted or fused pyrrolidine rings were synthesized using the cycloaddition, and can further undergo [1,3] N-to-C rearrangement to five-membered carbocycles with a different palladium catalyst. The utility of the (3+2) cycloaddition is also demonstrated by the preparation of various derivatives from the bicyclic pyrrolidine products.

Fully substituted pyranones via quasi-heterogeneous genuinely ligand-free migita-stille coupling of iodoacrylates

Migita-Stille coupling of (Z)-?2-iodoacrylates with (E)-?±-stannyl allylic alcohols to furnish 5-alkylidene-4-substituted-5,6-dihydro-2H-pyran-2-ones is efficiently catalyzed by 2% Pd black in DMF, while Pd(PPh3)4 is inactive. Heterogeneous Pd released in solution is most likely responsible for the catalysis. The reaction is applicable to other substrates, without having to resort to ligands, additives, and/or solid support for Pd. The resulting pyranones can be rearranged to fully functionalized pyranones in another single step.

Stereoselective silylcupration of conjugated alkynes in water at room temperature

Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-β-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology. Fast, cheap, and green: Micellar catalysis enables the selective construction of a variety β-silyl-substituted carbonyl derivatives under mild aqueous conditions. The reaction is catalyzed by low levels of CuI, is compatible with numerous electron-withdrawing groups, affords high yields, and provides opportunities for scale-up and recycling of the reaction medium. The environmental impact, as measured by E Factors, is very low.

Platinum-catalyzed hydrosilylations of internal alkynes: Harnessing substituent effects to achieve high regioselectivity

Rule of thumb: The high yielding title reaction is described with a focus on understanding the factors that govern the regioselectivity of the process (see scheme). Electronic, steric, and functional group properties all influence the selectivity, an understanding of which allows the selective formation of trisubstituted vinylsilanes, which are synthetically useful compounds for accessing stereodefined alkenes. Copyright

Synthesis of demethylated nidulol via an intramolecular Michael reaction

An expeditious synthesis of 5,7-dihydroxy-6-methylphthalide from open-chain precursors is described. The key intermediates, synthons 3 and 4, were readily obtained from accessible materials and were further transformed to a common precursor, a five-membered lactone derivative, via an intramolecular Michael addition. Lactone 2 was aromatised to the phthalide system under basic conditions. The process thus constitutes a formal synthesis of the phthalide framework.

One-pot synthesis of trisubstituted monomethylated benzene-1,3-diols via a Michael addition-Dieckmann cyclization sequence from methyl (E)3-methoxy-4- methoxycarbonylbut-2-enoate anion and methyl alkynoates and its application to the total synthesis of nidulol

The reaction of methyl (E)3-methoxy-4-methoxycarbonylbut-2-enoate (1) with a number of methyl alkynoates under appropriate conditions gave the monomethylated trisubstituted resorcinol derivatives 3 in a regiocontrolled manner, via a Michael addition-Dieckmann cyclization sequence in one pot. The resorcinol 3d, prepared in this manner, was used as the starting material for a three step, highly efficient (54% from 3d) synthesis of the bioactive fungal metabolite nidulol (4). Georg Thieme Verlag Stuttgart.

Synthesis of a Pondaplin Dimer and Trimer. Aromatic Interactions in Novel Macrocycles

Synthetic challenges in the use of an oxabicyclo[2.2.2]octenone moiety as a masked arene for the synthesis of pondaplin are disclosed. During the course of a study of the Heck reaction as a tool for macrocyclization to provide strained paracyclophanes, no

Stannylcupration of γ-Heterosubstitued Acetylenic Esters: a New Route to 4-Stannylated Five Membered N- and O- Heterocycles.

4-Tributylstannyl,2-(5H)-furanone and pyrrolone have been prepared in good yields by addition of mixed stannylcuprate reagent on γ-amino and γ-hydroxy acetylenis esters.The use of these compounds as useful intermediates for the selective functionalization

Convenient synthesis of 4-methylene-2-oxazolidinones and 4-methylenetetrahydro-1,3-oxazin-2-ones via transition-metal catalyzed intramolecular addition of nitrogen atom to actylenic triple bond

2-Propynyl tosylcarbamates 1 undergo cyclization smoothly by the catalysis of CuCl/Et3N or AgNCO/Et3N to furnish 4-methylene-2-oxazolidinones 2 in good yields. The similar cyclization of the N-acyl derivatives of 1 (PhCO, MeCO, EtOCO, etc.) is catalyzed effectively by AgNCO/t-BuOK. These reactions accommodate a variety of substituents at C1 and C3 of 2-propyn-1-ol and provide (Z)-2 as single stereoisomers. The scope of the cyclization of 3-butynyl carbamates is rather limited, and in general only N-tosyl derivatives of terminally unsubstituted 3-butyn-1-ols undergo cyclization to give 4-methylenetetrahydro-1,3-oxazin-2-ones in synthetically useful yields by the catalysis of AgNCO/Et3N or AgNCO/t-BuOK.