851592-07-9Relevant academic research and scientific papers
Catalytic enantioselective 1,2-diboration of 1,3-dienes: Versatile reagents for stereoselective allylation
Kliman, Laura T.,Mlynarski, Scott N.,Ferris, Grace E.,Morken, James P.
supporting information; experimental part, p. 521 - 524 (2012/03/11)
More with boron: The development of catalytic enantioselective 1,2-diboration of 1,3-dienes enables a new strategy for enantioselective carbonyl allylation reactions (see scheme). These reactions occur with outstanding levels of stereoselection and can be applied to both monosubstituted and 1,1-disubstituted dienes. The carbonyl allylation reactions provide enantiomerically enriched functionalized homoallylic alcohol products. Copyright
New general method for regio- and stereoselective allylic substitution with aryl and alkenyl coppers derived from grignard reagents
Kiyotsuka, Yohei,Katayama, Yuji,Acharya, Hukuni P.,Hyodo, Tomonori,Kobayashi, Yuichi
supporting information; experimental part, p. 1939 - 1951 (2009/08/07)
Allylic substitution with sp2-carbon reagents (aryl and alkenyl anions) was realized by using allylic picolinates and copper reagents derived from RMgBr and CuBr-Me2S to afford anti SN2 products regioand stereoselectively. Steric and electronic factors in the reagents and the size of the methylene substituents around the allylic moiety marginally affected the selectivity. The reaction system was compatible with alkyl reagents as well. Furthermore, the substitution was applied to construction of a quaternary center and synthesis of (-)-sesquichamaenol. Electron-withdrawing nature of the pyridyl group and chelation of the C(=O)-C5H4N to MgBr2 generated in situ were found to be responsible for the high efficiency of the substitution.
Picolinoxy group, a new leaving group for anti SN2 selective allylic substitution with Aryl Anions Based on Grignard Reagents
Kiyotsuka, Yohei,Acharya, Hukum P.,Katayama, Yuji,Hyodo, Tomonori,Kobayashi, Yuichi
supporting information; experimental part, p. 1719 - 1722 (2009/04/10)
The picolinoxy group was found to be an extremely powerful leaving group for allylic substitution with aryl nucleophiles derived from ArMgBr and CuBr?Me2S. The substitution proceeds with anti SN2 pathway and with high chirality transfer. The electron-withdrawing effect of the pyridyl group and chelation to MgBr2 are likely the origin of success. Results suggesting these effects were obtained.
Superbase-promoted rearrangement of oxiranes to cyclopropanes
Mordini, Alessandro,Peruzzi, Daniela,Russo, Francesco,Valacchi, Michela,Reginato, Gianna,Brandi, Alberto
, p. 3349 - 3360 (2007/10/03)
Aryl- and alkenyl substituted oxiranes, when submitted to treatment with superbasic reagents, undergo a highly regio- and stereoselective rearrangement leading to cyclopropylmethanol derivatives. The process can also be applied to mono- and dihydroxy subs
