206983-90-6Relevant articles and documents
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 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
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
