18335-58-5Relevant academic research and scientific papers
A new strategy for the synthesis of himbacine
Casey, Mike,McCarthy, Robert
, p. 801 - 804 (2011/06/11)
A new strategy for the assembly of himbacine and analogues, which display potent biological activity, is described. A four-step route to a key intermediate has been developed, in which the key step is a highly diastereoselective Michael-Dieckmann domino reaction. Use of an enantioenriched Michael acceptor, readily obtained by an asymmetric dihydroxylation reaction, allowed kinetic resolution of the Michael donor, which was itself prepared by a domino reaction. Georg Thieme Verlag Stuttgart.
The products of hydrolysis of cyclic orthoesters as a function of pH and the theory of stereoelectronic control
Deslongchamps, Pierre,Lessard, Jean,Nadeau, Yves
, p. 2485 - 2492 (2007/10/02)
The acid hydrolysis of cyclic orthoesters 1, 3-6 (R=Me), and 2 (R=Me and Et) as a function of pH was studied.The bicyclic orthoester 5 yields mainly the hydroxy-ester (less than 5percent lactone), and this result is essentially independent of pH.For the other orthoesters, the relative percentage of products differs for each case and varies with pH.At pH3.These results are explained on the basis of the stereoelectronic theory for the cleavage of tetrahedral intermediates.
SN2 iodide displacement on unsymmetrical cyclic dioxenium salts. A stereoelectronically controlled reaction
Beaulieu, Normand,Deslongchamps, Pierre
, p. 164 - 167 (2007/10/02)
Iodide ion reacts with the cyclic dioxenium salts 1-6 to yield mixtures of iodoester and lactone plus alkyl iodide (Table 1).The formation of iodoester competing with the formation of lactone appears to be an unexpected result.It can, however, be explained by a stereoelectronic effect, similar to the anomeric effect in acetals, which is also responsible for the greater stability of the Z over the E form in dioxenium salts and in esters.
Oxidative cleavage of conformationally rigid vinyl orthoesters. Evidence for primary and secondary stereoelectronic control in the cleavage of tetrahedral intermediates
Deslongchamps, Pierre,Beaulieu, Normand,Chenevert, Robert,Dickinson, Robert A.
, p. 1051 - 1058 (2007/10/02)
Permanganate oxidation of either axial vinyl orthoester 1 or equatorial vinyl orthoester 7 yields essentially hydroxy ester 5 only.These results can be interpreted on the basis of stereoelectronic effects which control the cleavage of tetrahedral intermediates 2 and 8.
