654071-49-5Relevant academic research and scientific papers
Synthesis of optically active β- Or γ-alkyl-substituted alcohols through copper-catalyzed asymmetric allylic alkylation with organolithium reagents
Guduguntla, Sureshbabu,Fananas-Mastral, Martin,Feringa, Ben L.
, p. 8274 - 8280 (2013/09/24)
An efficient one-pot synthesis of optically active β-alkyl-substituted alcohols through a tandem copper-catalyzed asymmetric allylic alkylation (AAA) with organolithium reagents and reductive ozonolysis is presented. Furthermore, hydroboration-oxidation following the Cu-catalyzed AAA leads to the corresponding homochiral γ-alkyl-substituted alcohols.
Asymmetric synthesis of the fully elaborated pyrrolidinone core of oxazolomycin A
Donohoe, Timothy J.,O'Riordan, Timothy J. C.,Peifer, Manuel,Jones, Christopher R.,Miles, Timothy J.
, p. 5460 - 5463,4 (2012/12/12)
The asymmetric synthesis of the key pyrrolidinone core, including a highly elaborated exocyclic carbon chain, of the γ-lactam β-lactone antibiotic oxazolomycin A is described. Principal features include the Birch reduction of an aromatic pyrrole nucleus, a late stage RuO4 catalyzed pyrrolidine oxidation, and a highly diastereoselective organocerium addition to an aldehyde.
Asymmetric synthesis of the fully elaborated pyrrolidinone core of oxazolomycin A
Donohoe, Timothy J.,O'Riordan, Timothy J. C.,Peifer, Manuel,Jones, Christopher R.,Miles, Timothy J.
, p. 5460 - 5463 (2013/01/15)
The asymmetric synthesis of the key pyrrolidinone core, including a highly elaborated exocyclic carbon chain, of the γ-lactam β-lactone antibiotic oxazolomycin A is described. Principal features include the Birch reduction of an aromatic pyrrole nucleus, a late stage RuO4 catalyzed pyrrolidine oxidation, and a highly diastereoselective organocerium addition to an aldehyde.
Catalytic asymmetric carbong-carbon bond formation via allylic alkylations with organolithium compounds
Perez, Manuel,Fananas-Mastral, Martin,Bos, Pieter H.,Rudolph, Alena,Harutyunyan, Syuzanna R.,Feringa, Ben L.
experimental part, p. 377 - 381 (2012/01/06)
Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbon bond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.
High diversity on simple substrates: 1,4-dihalo-2-butenes and other difunctionalized allylic halides for copper-catalyzed SN2′ reactions
Falciola, Caroline A.,Alexakis, Alexandre
supporting information; experimental part, p. 10615 - 10627 (2009/12/07)
Enantioselective allylic alkylation with an organomagnesium reagent catalyzed by copper thiophene carboxylate (CuTC) was carried out on difunctionalized substrates, such as commercially available 1,4-dichloro-2- butene and 1,4-dibromo-2-butene, and on similar compounds of higher substitution pattern of the olefin for the formation of all-carbon chiral quaternary centers. The high regioselectivity obtained throughout the reactions favored good regiocontrol for the addition of phenyl Grignard reagents. Other difunctionalized substrates (allylic ethers and allylic alcohols) also underwent asymmetric SN2′ substitution.
Catalytic enantioselective synthesis of vicinal dialkyl arrays
Van Zijl, Anthoni W.,Szymanski, Wiktor,Lopez, Ferrnando,Minnaard, Adriaan J.,Feringa, Ben L.
supporting information; experimental part, p. 6994 - 7002 (2009/05/09)
(Chemical Equation Presented) With a consecutive "asymmetric allylic alkylation (AAA)/cross-metathesis (CM)/conjugate addition (CA)" protocol it is possible to synthesize either stereoisomer of compounds containing a vicinal dialkyl array with excellent stereoselectivity. The versatility of this protocol in natural product synthesis is demonstrated in the preparation of the ant pheromones faranal and lasiol.
Synthesis of optically active bifunctional building blocks through enantioselective copper-catalyzed allylic alkylation using Grignard reagents
Van Zijl, Anthoni W.,Lopez, Fernando,Minnaard, Adriaan J.,Feringa, Ben L.
, p. 2558 - 2563 (2007/10/03)
Enantioselective copper-catalyzed allylic alkylations were performed on allylic bromides with a protected hydroxyl or amine functional group using several Grignard reagents and Taniaphos L1 as a ligand. The terminal olefin moiety in the products was transformed into various functional groups without racemization, providing facile access to a variety of versatile bifunctional chiral building blocks.
Highly enantioselective Cu-catalysed allylic substitutions with Grignard reagents
Lopez, Fernando,Van Zijl, Anthoni W.,Minnaard, Adriaan J.,Feringa, Ben L.
, p. 409 - 411 (2008/02/05)
A catalyst system able to perform highly enantioselective Cu-catalysed allylic alkylations with Grignard reagents is described. The Royal Society of Chemistry 2006.
Rhodium-Catalyzed Methylenation of Aldehydes
Lebel, Helene,Paquet, Valerie
, p. 320 - 328 (2007/10/03)
The rhodium-catalyzed methylenation of aldehydes using trimethylsilyldiazomethane and triphenylphosphine produces a variety of terminal alkenes in excellent yields. These mild and nonbasic reaction conditions allow the conversion of enolizable substrates (keto aldehydes and nonracemic α-substituted aldehydes) to terminal alkenes without epimerization. Optimization of the reaction conditions led to the conclusion that a variety of rhodium(I) sources can be used as catalysts. The effect of the solvent on the reaction has also been studied, and it indicates that although the THF is the best solvent, other solvents may be used. The reactivity of the system is very much dependent on the nature of the phosphine reagent. The use of an easily removable phosphine is also described. Spectroscopic studies indicate that the reaction proceeds via an unusual mechanism which leads to the in situ formation of the salt-free phosphorus ylide, methylenetriphenylphosphorane.
