54125-02-9

Usage

Uses

Used in Pharmaceutical Synthesis:
1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE is used as a reagent in the Mannich-Michael reaction for the synthesis of piperidinones and enaminones. These compounds are important building blocks in the development of various pharmaceuticals, particularly those targeting the central nervous system and other therapeutic applications.
Used in Organic Synthesis:
As a Diels-Alder diene, 1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE is employed in the synthesis of various heterocyclic compounds, such as pyridones, pyranones, sulfone analogues of griseofulvin (sulfogriseofulvins), 4H-1-aminopyrroles, and 4,5H-pyrazoles. These compounds have diverse applications in the fields of pharmaceuticals, agrochemicals, and materials science.
Used in Asymmetric Hetero-Diels-Alder Cyclization:
1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE is used in asymmetric hetero-Diels-Alder cyclization reactions, where it reacts with benzaldehyde in the presence of mesoporous inorganic/metalorganic hybrid materials as catalysts. This process allows for the selective formation of complex heterocyclic structures with potential applications in the development of novel pharmaceuticals and other specialty chemicals.
Used in Mukaiyama-Michael-type Addition/Heterocyclization:
1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE is also utilized in Mukaiyama-Michael-type addition/heterocyclization reactions with 1,2-diaza-1,3-butadiene. This reaction provides access to a range of nitrogen-containing heterocycles, which are valuable intermediates in the synthesis of biologically active compounds and advanced materials.

Purification Methods

It may contain up to 1% of the precursor 4-methoxybut-4-ene-2-one. It is easily purified by distilling through a Vigreux column (p 11) in a vacuum and taking the middle fraction. [Danishefsky & Kitihara J Am Chem Soc 96 7807 1974, Danishefsky Acc Chem Res 14 400 1981.]

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 51731-17-0 trans-4-methoxy-3-buten-2-one 
• 4652-27-1 4-methoxy-3-buten-2-one 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 

Downstream Products

• 54125-08-5 4-methyl-4-formylcyclohex-2-enone 
• 62680-12-0 trans-1-Methoxy-4-phenylsebnobut-1-en-3-on 
• 1523-89-3 methyl 1-methyl-4-oxo-2-cyclohexene-1-carboxylate 
• 72475-99-1 3-Methoxy-4-methyl-4-carbomethoxycyclohexanon 
• 127131-75-3 4-carbomethoxy-3-methoxy-4-methyl-1-<(trimethylsilyl)oxy>cyclohex-1-ene 
• 71094-25-2 C₁₉H₁₈N₄O₆ 
• 51731-17-0 trans-4-methoxy-3-buten-2-one 
• 83043-44-1 2-<(Trimethylsilyl)oxy>thiophene 
• 91879-80-0 (1E,6E)-5-hydroxy-1-methoxy-7-phenylhepta-1,6-dien-3-one 
• 91879-81-1 (1E,6E)-1-Methoxy-7-phenyl-5-trimethylsilanyloxy-hepta-1,6-dien-3-one 
• 83095-28-7 (E)-4-Methoxy-1-[6-((E)-styryl)-4-trimethylsilanyloxy-5,6-dihydro-2H-pyran-2-yl]-but-3-en-2-one 
• 85613-04-3 2-(E-styryl)-2,3-dihydro-4H-pyran-4-one 
• 190835-53-1 (+)-(S)-2-(trans-β-styryl)-2,3-dihydro-pyran-4-one 
• 139627-54-6 (R)-2-(E)-styryl-2,3-dihydro-4H-pyran-4-one 

Relevant academic research and scientific papers

Unexpected regioselectivity in the synthesis of pyranonaphthoquinone via the diels-alder reaction

The unusual regioselectivity In the Diels-Alder reactions of pyranoquinone 1 with (4,4-dlmethoxybuta-1,3-dlen-2-yloxy)trimethylsilane 2 are explored by both computations and experiments. The regioselectivity Is controlled by the electrostatic interaction of the lactone ring-oxygen and the vicinal quinone oxygen on the transition structure, which can be tuned by the terminal methyl group of the butadienes.

PEG-polymer-supported liquid-phase combinatorial synthesis of structurally diverse 2,3-dihydro-4-pyridones

A convenient liquid-phase synthetic protocol for the construction of structurally diverse 2,3-dihydro-4-pyridones on soluble polymer support by the aza Diels-Alder reaction has been developed, which utilized a one-pot three-component reaction of either PEG-supported amine, aromatic aldehydes and the Danishefsky's diene, or PEG-supported aldehyde, aromatic amines and Danishefsky's diene.

Enantioselective Formal [4+1] Cycloaddition of Diazoarylacetates and the Danishefsky's Diene: Stereoselective Synthesis of (-)-1,13-Herbertenediol

Rodium chiral diene complex-catalyzed enantioselective cycloaddition of aryl α-diazoarylacetates and electron-enriched Danishefsky-type dienes afforded highly functionalized and optically enriched cyclopentenones in excellent yields (up to 97% yield) and

Total Synthesis of (±)-Furanether A

The first total synthesis of (±)-furanether A, which exhibits good antifeedant activity, has been concisely achieved in 13 linear steps. Notably, the key rigid tetracyclic skeleton containing a 1-methyl-8-oxabicyclo[3.2.1]octane moiety with two vicinal quaternary carbon centers was rapidly constructed in one step through a unique tandem C-H oxidation/oxa-[3,3] Cope rearrangement/aldol cyclization sequence.

Synthesis of a functionalized 7,6-bicyclic spiroimine ring fragment of the spirolides

The asymmetric synthesis of a functionalized 7,6-spiroimine related to the spirolides is described. Intermolecular Diels-Alder cycloaddition of a chiral trisubstituted dienophile and Danishefsky's diene enabled simultaneous installation of the C7 and C29 stereocenters. Further transformations and late-stage aza-Wittig cyclization afforded the spiroimine in good yield. During this study, an unprecedented 14-membered dialdimine was also obtained.

Synthesis and NMDA-receptor affinity of 4-oxo-dexoxadrol derivatives

A synthesis of novel dexoxadrol analogues is described, which allows modifications of the piperidine substructure. The key step of the synthesis is a hetero Diels-Alder reaction of the imine 12 with Danishefsky's diene 6. After separation of the diastereo

One pot solid phase synthesis of 2-substituted 2,3-dihydropyridin-4(1H)- ones on Rinkamide-resin

A novel solid phase synthesis of 2-substituted 2,3-dihydropyridin-4(1H)- ones using Rinkamide-polystyrene-resin is described. The key step involves a hetero-Diels-Alder reaction of Danishefsky's diene with solid phase bound imines, which was carefully opt

Chiral hetero Diels-Alder products by enantioselective and diastereoselective zirconium catalysis. Scope, limitation, mechanism, and application to the concise synthesis of (+)-prelactone C and (+)-9-deoxygoniopypyrone

Catalytic asymmetric hetero Diels-Alder (HDA) reactions using a chiral zirconium complex have been developed. The reactions of aldehydes with Danishefsky's dienes proceeded smoothly to afford the corresponding pyranone derivatives in high yields with high diastereo- and enantioselectivities in the presence of a chiral zirconium complex, which was prepared from zirconium tert-butoxide, (R)-3,3′-diiodobinaphthol or its derivative, a primary alcohol, and a small amount of water. It is noted that 2,3-trans-pyranone derivatives were obtained with remarkably high diastereo- and enantioselectivities in the reaction with 4-methyl Danishefsky's diene. This is the first example of catalytic asymmetric trans-selective hetero Diels-Alder reactions of aldehydes. Furthermore, asymmetric HDA reactions with 4-benzyloxy Danishefsky's dienes were conducted to afford 2,3-cis-pyranone derivatives in high selectivities. Isolation of an intermediate of this asymmetric hetero Diels-Alder reaction indicated that the reaction proceeded in a stepwise cycloaddition pathway. Finally, these catalytic, asymmetric hetero Diels-Alder reactions were successfully applied to concise syntheses of biologically important natural pyranone derivatives, (+)-Prelactone C and (+)-9- deoxygoniopypyrone.

An Efficient and Highly Chemoselective Method to Desilylate Silyl Ethers

An efficient and highly chemoselective desilylating method is described.Trimethylsilyl ethers (0.25 M) in a CH3OH/CCl4 (1:1) solvent mixture are deprotected to their corresponding alcohols with ultrasound in a commercial ultrasonic cleaning bath.Selective deprotection of tert-butyldimethylsilyl ethers of benzyl alcohols and phenols is achieved under ultrasonic conditions.We deprotected also tert-butyldimethylsilyl ethers of primary alcohols, whereas tert-butyldimethylsilyl ethers of secondary and tertiary alcohols are stable under these conditions. - Key words: Sonochemistry; Ultrasound; Cavitation; Desilylation; Chemoselection; Deprotection.