27749-07-1Relevant academic research and scientific papers
Intramolecular azide-alkene 1,3-dipolar cycloaddition/enamine addition(s) cascade reaction: Synthesis of nitrogen-containing heterocycles
De Miguel, Irene,Herradon, Bernardo,Mann, Enrique
supporting information; experimental part, p. 1731 - 1736 (2012/07/28)
A cascade intramolecular azide-alkene 1,3-dipolar cycloaddition/1,2 enamine and/or 1,4 enamine addition reaction sequence has been developed, and provides access to a variety of nitrogen containing heterocycles from readily available ω-azido alkenes. Copy
A model study for the total synthesis of (±)-scopadulin: Stereoselective construction of the A/B ring system with desired functionalities
Abdur Rahman,Ohno, Hiroaki,Yoshino, Hitoshi,Satoh, Norifumi,Tsukaguchi, Mahoto,Murakami, Kazuo,Iwata, Chuzo,Maezaki, Naoyoshi,Tanaka, Tetsuaki
, p. 127 - 134 (2007/10/03)
A model study toward the total synthesis of (±)-scopadulin is described. Stereocontrolled synthesis of the A/B ring system with desired functionalities was achieved by stereoselective cyanation of a bicyclic enone with Et2AlCN, diastereoselective construction of a quaternary carbon at C-4 with LDA-BOMCl, and conversion of the cyano group into a methyl group.
A Facile Synthesis of Bicycloalkan-1-ols. Evidence for Organosamarium Intermediates in the Samarium(II) Iodide Promoted Intramolecular Barbier-Type Reaction
Molander, Gary A.,McKie, Jeffrey A.
, p. 4112 - 4120 (2007/10/02)
Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicycloalkan-1-ols.Thus, a variety of 3-(ω-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic q
The Role of BF3*Et2O in Reactions of Lower Order (Gilman) Organocuprates
Lipshutz, Bruce H.,Ellsworth, Edmund L.,Siahaan, Teruna J.
, p. 1351 - 1358 (2007/10/02)
The effects of BF3*Et2O on lower order organocuprate reactions in THF have been investigated so as to determine what factors are responsible for the oftentimes dramatic reaction-rate enhancements observed.From spectroscopic experiments on the reagents alone, supported further by chemical studies, it was found that an orginally formed cuprate (R2CuLi or RR'CuLi) is altered significantly upon exposure to this Lewis acid.The copper-containing species thereby generated, together with BF3, form a more reactive combination and appear to be at least in part responsible forthe accelerated chemistry.
EFFECT OF GEGENIONS ON ORGANOCUPRATE REACTIVITY/SELECTIVITY: HIGHER ORDER, MIXED LITHIO-SODIO CYANOCUPRATES
Lipshutz, Bruce H.,Ellsworth, Edmund L.,Behling, James R.,Campbell, Arthur L.
, p. 893 - 896 (2007/10/02)
Several different types of reactions characteristic of organocuprates have been studied using reagents RTRRCu(CN)LiNa derived from CuCN and one equivalent each of an organolithium (RTLi) and organosodium (RRNa) species.
REACTIONS OF STOICHIOMETRIC HIGHER ORDER, MIXED LITHIO MAGNESIO ORGANOCUPRATES
Lipshutz, Bruce H.,Parker, David A.,Nguyen, Sam L.,McCarthy, Keith E.,Barton, John C.,et al.
, p. 2873 - 2880 (2007/10/02)
Novel higher order cuprates, R(2-thienyl)Cu(CN)LiMgBr (2), are prepared from the 1:1:1 combination of CuCN, 2-lithiothiophene and RMgX.Reactions of various members of this new class of reagents are described, including substitution and conjugate addition processes, where the ligand derived from the Grignard reagent is selectively transferred.The effects of added BF3*Et2O are discussed.Some comparison reactions with the corresponding lower order reagents, RCu(CN)MgBr, have also been carried out.Evidence is presented suggesting that species 2, unlike their dilithio analogs, are not discrete.
MORE HIGHLY MIXED, HIGHER ORDER CYANOCUPRATES "rt(2-thienyl)Cu(CN)Li2". EFFICIENT REAGENTS WHICH PROMOTE SELECTIVE LIGAND TRANSFER
Lipshutz, Bruce H.,Kozlowski, Joseph A.,Parker, David A.,Nguyen, Sam L.,McCarthy, Keith E.
, p. 437 - 448 (2007/10/02)
The combination of an organolithium (RTLi) and 2-lithiothiophene (2-thienyl) with CuCN forms a new reagents, "RT(2-thienyl)Cu(CN)Li2".This species selectively transfers the RT ligand in substitution reactions with epoxides and halides.In conjugate addition processes, the cuprate reacts with unhindered substrates, while β,β-disubstituted cases unexpectedly afford products resulting from 1,2-addition of the thiophene group.The prospects for use of these reagents in the synthesis of polyene macrolide antibiotics are discussed.
EFFECTS OF LEWIS ACIDS ON HIGHER ORDER, MIXED CUPRATE COUPLINGS
Lipshutz, Bruce H.,Parker, David A.,Kozlowski, Joseph A.,Nguyen, Sam L.
, p. 5959 - 5962 (2007/10/02)
The presence of BF3*Et2O in reactions of R2Cu(CN)Li2 and RT(2-thienyl)Cu(CN)Li2 with epoxides and α,β-unsaturated ketones leads to dramatic enhancements in reaction rates and/or product yields relative to those observed in the absence of this L
Conjugate Addition Reactions of α,β-Unsaturated Ketones with Higher Order, Mixed Organocuprate Reagents, R2Cu(CN)Li2
Lipshutz, Bruce H.,Wilhelm, Robert S.,Kozlowski, Joseph A.
, p. 3938 - 3942 (2007/10/02)
Conjugate reactions of mixed cuprates R2Cu(CN)Li2 with α,β-unsaturated ketones are reported.These reagents, in most cases, react extremely rapidly affording the corresponding alkylated ketones in high yields.Attempts at trapping the intermediate enolates appeared to be successful using MeI as electrophile; however, the method is not general and was, therefore, not pursued.The effects of solvent and ligand composition on R2Cu(CN)Li2 as well as on the more highly mixed species RTRRCu(CN)Li2 have been examined.The selectivity of ligand transfer in these latter,second generation organocuprates is also discussed.
