62217-47-4

Upstream product

• 107-86-8 3,3-dimethyl acrylaldehyde 
• 6921-34-2 benzylmagnesium chloride 
• 870-63-3 prenyl bromide 
• 100-52-7 benzaldehyde 
• 117785-56-5 (CH₃)2CCHCH(tributylstannyl)CH₂Ph 
• 513-37-1 2-methylprop-1-enyl chloride 
• 2245-69-4 potassium 2-phenethyl oxide 

Downstream Products

• 1326344-05-1 C₂₁H₂₅BrO₃ 

Relevant academic research and scientific papers

Enantioselective Conjunctive Cross-Coupling of Bis(alkenyl)borates: A General Synthesis of Chiral Allylboron Reagents

Palladium-catalyzed conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.

Electrochemical intramolecular aminooxygenation of unactivated alkenes

An electrochemical approach to the intramolecular aminooxygenation of unactivated alkenes has been developed. This process is based on the addition of nitrogen-centered radicals, generated through electrochemical oxidation, to alkenes followed by trapping of the cyclized radical intermediate with 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO). Difunctionalization of a variety of alkenes with easily available carbamates/amides and TEMPO affords aminooxygenation products in high yields and with excellent trans selectivity for cyclic systems (d.r. up to>20:1). The approach provides a much-needed complementary route to existing cis-selective methods.

Development of an intramolecular aryne ene reaction and application to the formal synthesis of (±)-crinine

A general and high yielding annulation strategy for the synthesis of various carbo- and heterocycles, based on an intramolecular aryne ene reaction is described. It was found that the geometry of the olefin is crucial to the success of the reaction, with exclusive migration of the trans-allylic-H taking place. Furthermore, the electronic nature of the aryne was found to be important to the success of the reaction. Deuterium labeling studies and DFT calculations provided insight into the reaction mechanism. The data suggests a concerted asynchronous transition state, resembling a nucleophilic attack on the aryne. This strategy was successfully applied to the formal synthesis of the ethanophenanthridine alkaloid (±)-crinine.

Intramolecular aryne-ene reaction: Synthetic and mechanistic studies

Although the chemistry of arynes is well developed, some challenges still remain. The ene reaction of arynes has not gained widespread use in synthesis as a result of poor yields and selectivity. A general, high yielding and selective intramolecular aryne-ene reaction is described providing various benzofused carbo- and heterocycles. Mechanistic data is presented, and a rationale for the resulting stereochemistry is discussed.

[2,3] Sigmatropic rearrangement of unstable sulfur ylides from allyl sulfonium salts. Comparative study of electrochemical reduction with the base method and mechanism elucidation by the MO method

The cathodic reduction of sulfonium salts in acetonirile under the presence and absence of benzaldehyde were carried out and compared with the results of the base method. Under the presence of benzaldehyde, the electrochemical reduction gave epoxides as a

A Convenient Method for the Transformation of Allylstannanes to Alcohols, Ethers, Esters, and Amines

Allylstannanes were easily oxidized with copper(II) bromide in the presence of water, alcohols, and sodium acetate to give the corresponding allylic alcohols, ethers, and acetates, respectively.The allylic amines were also obtained by the succesive treatm

Stereochemical Aspects in the Insertion by Alkylidenemethylene Carbenoids into the α-C-H Bond of Alkoxides

Primary alkoxides (R1CH2OM; M=K or Li) when treated with haloalkenes (R3R4C=CXY; X=Cl or Br, Y=H or Cl) in the presence of n-BuLi in THF at 0 deg C gave allylic alcohols (R1CH(OH)CH=CR3R4) through the insertion reaction of the corresponding alkylidenemethylene carbenoid () into the α-C-H bond of alkoxides.Secondary alkoxides (R1R2CHOM), under similar reaction conditions, gave butyl adducts (R1R2C(OH)C4H9) in addition to the insertion products.In particular, the C-H insertion of menthyl oxide proceeded without stereospecificity to give a mixture of the axial and equatorial insertion products.These results provided evidence for the hydride abstraction-recombination mechanism in the carbenoid insertion reaction.The regioselective, nonstereospecific insertion reaction was also observed when alkoxides were treated with separately prepared ((2,3-benzo-2-cyclohexylidene)chloromethyl)lithium at temperatures from -95 to -40 deg C.The absence of H-D scrambling in crossover experiments under these reaction conditions clearly showed that the hydride abstraction-recombination mechanism proceeded within a solvent cage.An inversion of configuration on the carbenoid carbon in the hydride abstraction step was proposed on the basis of the E/Z stereoselectivity in the insertion products.