29290-99-1

Upstream product

• 6386-71-6 isopropenyllithium 
• 98-86-2 acetophenone 
• 21578-99-4 rac-α,β,β-trimethylstyrene oxide 
• 769-57-3 α,β,β-trimethylstyrene 
• 557-93-7 2-bromoprop-1-ene 
• 1068-55-9 isopropylmagnesium chloride 
• 563-80-4 3-methyl-butan-2-one 
• 13291-18-4 isopropenylmagnesium bromide 
• 814-78-8 3-Methyl-3-buten-2-one 
• 591-51-5 phenyllithium 

Downstream Products

• 17798-83-3 1-Chlor-2-methyl-2-phenyl-butanon-⁽³⁾ 
• 16939-15-4 3-methyl-4-phenylthiophene 
• 83125-20-6 2,5-dibromo-3-methyl-4-phenylthiophene 
• 18476-73-8 (3-methylbuta-1,3-dien-2-yl)benzene 
• 1072874-94-2 (E)-(4-chloro-3-methylbut-2-en-2-yl)benzene 
• 17798-86-6 4-bromo-3-methyl-3-phenyl-2-butanone 

Relevant academic research and scientific papers

α-Quaternary Mannich Bases through Copper-Catalyzed Amination-Induced 1,2-Rearrangement of Allylic Alcohols

A novel copper-catalyzed amination-induced 1,2-rearrangement reaction of allylic alcohols has been developed under simple and mild conditions. The commercially available N-fluorobenzenesulfonimide (NFSI) is employed as an amination reagent. In this transformation, not only alkyl, but also aryl substituents can efficiently undergo 1,2-carbon atom migration, thereby providing an efficient and powerful route to prepare a wide range of α-quaternary Mannich bases. The reaction features a broad substrate scope, operational simplicity, and excellent practicality.

Titanocene-promoted eliminations on epoxy alcohols and epoxy esters

The reaction of a series of 2,3-epoxy alcohols and the corresponding formates, acetates, and benzoates promoted by Cp2TiCl has been studied. The different outcome of the reaction of epoxy derivatives has been rationalized in terms of mechanistically biased processes. After homolytic oxirane cleavage, four main types of reaction were found: dehydroxylation, decarboxylation, dehydrogenation, and deoxygenation. The reaction products varied according to the substitution pattern. The radical nature of these eliminations is demonstrated.

One-pot formation of allylic chlorides from carbonyl derivatives

(Chemical Equation Presented) An efficient, one-pot method for the conversion of carbonyl electrophiles to allylic chlorides has been developed, by activating magnesium alkoxides in situ using TiCl4.

Synthesis of conjugated γ- and δ-lactones from aldehydes and ketones via a vinylation(allylation)-ring closing metathesis-oxidation sequence

Nucleophilic C-vinylation and C-allylation of aldehydes and ketones followed by O-allylation of the obtained carbinols gave the corresponding allyl or homoallyl ethers, respectively. Ring-closing metathesis of these compounds afforded in many cases cyclic ethers (dihydrofurans and dihydropyrans, respectively) bearing disubstituted and trisubstituted C=C bonds. These were then subjected to allylic oxidation to yield conjugated γ- and δ-lactones. Reasons for the observed failures are presented and discussed.

MECHANISTIC STUDY ON THE PHOTO-OXIDATION OF α-DIKETONES. INTERACTION OF TRIPLET α-DIKETONES WITH OXYGEN

The mechanism for photo-oxidation of α-diketones in the presence of olefins has been studied, focusing on the interaction of triplet diketones with O2.Two types of reactions occur competitively.One is the formation of 1O2 by energy transfer to O2 and the other is the addition of O2 to triplet diketone, which yields acylperoxy radicals leading to the radical epoxidation of olefins.Ratios of the two reactions were determined from the yields of 1O2 products and epoxides.For most diketones, quantum yields for 1O2 formation were considerably high, in the range 0.3-0.8; but the yields for epoxides were in a wider range of 0.001-0.5.While the ratios of 1O2 formation and O2 addition to triplet diketones ranged from 29:71 for biacetyl to 1:99 for mesitil, the ratios remained constant by changing solvents or temperature.The latter O2 addition reaction decreased in the order of MeCOCOMe > PhCOCOMe > PhCOCOPh but the effect of m- and p-substituents on benzils was not significant, indicating the addition of O2 as a neutral biradical.In exceptional cases, the O2 addition was not effective for sterically inaccessible mesitil and some cyclic α-diketones.The mechanism of 1O2 formation was discussed in comparison to other carbonyl compounds.

Substitution Reactions of Secondary Halides and Epoxides with Higher Order, Mixed Organocuprates, R2Cu(CN)Li2: Synthetic, Stereochemical, and Mechanistic Aspects

Higher order cuprates, represented by the general formula R2Cu(CN)Li2, are readily prepared from copper cyanide and 2 equiv of an organolithium.These novel reagents react readily and efficiently with secondary unactivated iodides and bromides affording products of substitution.Likewise, mono-, di-, and trisubstituted epoxides undergo ring opening leading to the corresponding alcohols in excellent yields.The effects of solvent, temperature, gegenion, and variations in ligands are discussed.Replacement of the second equivalent of RLi by CH3Li strongly encouragestransfer of R over CH3 in R(CH3)Cu(CN)Li2 with halides.Use of PhLi as RRLi in place of one RTLi (i.e.RT(Ph)Cu(CN)Li2) is suggested for oxirane cleavage.The stereochemical implications associated with both couplings are also addressed.