3645-01-0Relevant articles and documents
The Hydroboration of 3-Chloro-1-iodo-1-propyne with Dialkylboranes, and its Application to the Syntheses of Some Geminally Dialkylated Propene Derivatives
Masuda, Yuzuru,Hoshi, Masayuki,Arase, Akira
, p. 3294 - 3299 (1992)
3-Chloro-1-iodo-1-propyne is smoothly hydroborated with dialkylboranes, giving (Z)-(3-chloro-1-iodo-1-propenyl)dialkylboranes exclusively.Subsequent treatment of the hydroboration mixture with sodium methoxide or aqueous sodium hydroxide results in migration of two alkyl groups from the boron atom to the α-alkenyl carbon atom to provide dialkylated allylboranes, which are protonolyzed with methanol or water to produce 1,1-dialkyl-1-propenes.Oxidation of the allylboranes with alkaline hydrogen peroxide prior to protonolysis gives 1,1-dialkyl-2-propen-1-ols.Treatmentof (Z)-(3-chloro-1-iodo-1-propenyl)dicyclohexylborane with Grignard reagents, followed by protonolysis with acetic acid, provides 3-alkyl-3-cyclohexyl-1-propenes in which the alkyl group is derived from Grignard reagent.
Cobalt-catalyzed reductive allylation of alkyl halides with allylic acetates or carbonates
Qian, Xin,Auffrant, Audrey,Felouat, Abdellah,Gosmini, Corinne
supporting information; experimental part, p. 10402 - 10405 (2011/12/03)
An efficient method for the direct allylation of alkyl halides catalyzed by simple cobalt(II) bromide has been developed. This reaction, using a variety of substituted allylic acetates or carbonates, provides the linear product as the major product. It displays broad substrate scope and good functional group tolerance. Copyright
Copper catalyzed magnesium-Barbier reaction for γ-selective alkyl-allyl coupling
Erdik, Ender,Ko?o?lu, Melike
, p. 4211 - 4214 (2008/02/08)
CuCN catalyzed alkyl-allyl coupling under magnesium-Barbier conditions occurs regioselectively and affords predominantly the γ-products in good to high yields. This one-pot CuCN catalyzed reaction utilising Mg, an alkyl halide and an allylic substrate in THF at room temperature provides an easy alternative to the classical CuCN catalyzed γ-allylation of alkyl Grignard reagents.
Ni-catalyzed alkylative dimerization of vinyl Grignard reagents using alkyl fluorides
Terao, Jun,Watabe, Hiroyasu,Kambe, Nobuaki
, p. 3656 - 3657 (2007/10/03)
Alkyl halides underwent unique cross-coupling reaction with vinylmagnesium chloride in the presence of Ni catalyst to give 2-alkyl-3-butenyl Grignard reagent (1) in high yields. This reaction proceeded efficiently at 25 °C in THF using primary and seconda
Enantioselective copper-mediated allylic substitution with Grignard reagents employing a chiral reagent-directing leaving group
Breit, Bernhard,Breuninger, Daniel
, p. 147 - 157 (2007/10/03)
Enantioselective copper-mediated allylic substitution with Grignard reagents was achieved employing the ortho-diphenylphosphanylferrocene carboxylate (o-DPPF) system as a planar chiral reagent-directing leaving group. Careful optimization of reaction parameters resulted in excellent regioselectivities and enantioselectivies of up to 95% ee.
Convenient Synthesis of Diene-Zirconocenes and Regioselective Partial Reduction of the More Highly Substituted Double Bonds of Conjugated Dienes via Complexation with Zirconocenes and Protonolysis
Maye, John P.,Negishi, Ei-ichi
, p. 1830 - 1831 (2007/10/02)
Conjugated dienes can be initially converted to their zirconocene complexes most conveniently by their reaction with (C5H5)2ZrCl2 and freshly ground Mg; the resultant complexes can then be protonolysed with 3 mol dm-3 HCl to give regioselectively monoenes corresponding to partial hydrogenation of the more highly substituted double bond.
AN EASY SYNTHESIS OF THE 2-PHENYLSULFONYL-SUBSTITUTED ALLYLIC BROMIDES AND ACETATES AND THEIR REACTIVITY TOWARDS NUCLEOPHILES
Auvray, P.,Knochel, P.,Normant, J. F.
, p. 5095 - 5098 (2007/10/02)
The reaction of phenyl vinyl sulfone with various aldehydes in the presence of a catalytic amount of DABCO furnishes in good yields the corresponding 2-phenylsulfonyl-substituted alcohols 5a-5e which can be easily converted into their acetates 2a-2b or into their allylically rearranged bromides 3a-3d.These reagents, in turn, react with nucleophiles (ketone enolates and cuprates) with an allylic rearrangement (SN2' mechanism) to give the functionalized unsaturated sulfones 6a-g and 7a-g.A palladium catalyzed reaction allows a stereo-controlled transformation of the sulfone 6b into the (Z,Z) skipped 1,4-diene 8.
