206983-90-6Relevant academic research and scientific papers
Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study
Barker, Graeme,Johnson, David G.,Young, Paul C.,Macgregor, Stuart A.,Lee, Ai-Lan
supporting information, p. 13748 - 13757 (2015/09/22)
Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that Erode the efficiency of chirality transfer become competitive.
The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex
Mukherjee, Paramita,Widenhoefer, Ross A.
supporting information, p. 3437 - 3444 (2013/07/05)
A 1:1 mixture of [AuCl(IPr)] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2- ylidine) and AgClO4 catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to for
The stereochemical course and mechanism of the IspH reaction
Citron, Christian A.,Brock, Nelson L.,Rabe, Patrick,Dickschat, Jeroen S.
, p. 4053 - 4057 (2012/06/01)
On the right path: The stereochemcial course of the IspH reaction, the last reaction in the deoxyxylulose phosphate pathway to terpenes, was investigated in feeding experiments with deuterated isotopologues of 1-deoxy-D-xylulose. The results support an enzyme mechanism for IspH that involves a previously suggested metallacyclopropane intermediate. Copyright
Diastereoselective zinco-cyclopropanation of chiral allylic alcohols with gem-dizinc carbenoids
Fournier, Jean-Francois,Mathieu, Simon,Charette, Andre B.
, p. 13140 - 13141 (2007/10/03)
The highly diastereoselective zinco-cyclopropanation of chiral allylic alcohols using gem-dizinc carbenoids is described. The reaction produces three contiguous stereogenic centers, and the resulting chiral cyclopropylzinc derivatives can be trapped with
Studies on the biosynthesis of the antibiotic moenomycin A
Schuricht, Urs,Endler, Kirsten,Hennig, Lothar,Findeisen, Matthias,Welzel, Peter
, p. 761 - 772 (2007/10/03)
Feeding experiments (13C and 15N-labeled precursors) shed light on the biosynthetic origin of the chromophore (unit A of 1), the N-acetyl groups, the 4-C-methyl group of the moenuronamide unit (part F of 1), the sugar units, and the
New and efficient synthetic routes to 1-deoxy-D-xylulose
Giner, Jose-Luis
, p. 2479 - 2482 (2007/10/03)
The biochemically important deoxysugar 1-deoxy-D-xylulose was synthesized by improved methods. D-Tartaric acid is the starting material for a synthesis which proceeds via the intermediacy of 2,3,4-tribenzyl-D- threitol. Another, highly efficient route use, the Sharpless asymmetric dihydroxylation of 5-benzyloxy-3-penten-2-one as its key step. These syntheses are especially useful-for isotopic labelling.
Iron carbonyl-mediated homologous Michael reactions of γ-alkoxy alkenones
Zhou,Green
, p. 4497 - 4500 (2007/10/02)
Iron tetracarbonyl complexes of γ-benzyloxy-α,β-unsaturated ketones react with several nucleophiles in the presence of Lewis acids to give γ-substitution products. The allyltetracarbonyliron cation intermediates generated allow retention of configuration of the double bond.
