18964-38-0Relevant academic research and scientific papers
Ammonium-directed oxidation of cyclic allylic and homoallylic amines
Bond, Christopher W.,Cresswell, Alexander J.,Davies, Stephen G.,Fletcher, Ai M.,Kurosawa, Wataru,Lee, James A.,Roberts, Paul M.,Russell, Angela J.,Smith, Andrew D.,Thomson, James E.
supporting information; experimental part, p. 6735 - 6748 (2009/12/31)
(Chemical Equation Presented) The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl3CCO2H gives exclusively the corresponding syn-epoxide for the 5-membered ring (>99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(Nbenzylamino) methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the correspondingN-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane- 1,2-diol with high levels of diastereoselectivity (g90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.
Stereodirecting effects in the characterization of ylide intermediates in reactions of singlet methylene with an allylic ether and an allylic chloride
Cubbage, Jerry W.,Edelbach, Brian L.,Kuen, Kan Shuh,DeLuca, JoAnn P.
, p. 9823 - 9834 (2007/10/03)
The stereodirecting effects of substrate substituents were examined in addition of 1:CH2 to the double bonds of 3-methoxycyclohexene (3a), 3-chlorocyclohexene (3b), and 3-methylcyclohexene (3c) in pentane solution at temperatures fro
Stereodirecting Effect of a Substrate Methoxy Substituent on the Addition of Singlet Methylene to a Double Bond
Young, Terry A.,O'Rourke, Colleen,Gray, Nathan B.,Lewis, Brian D.,Dvorak, Curt A.,et al.
, p. 6224 - 6228 (2007/10/02)
The stereodirecting effects of substrate methoxy, hydroxy, methylthio, and methyl substituents were examined in the addition of 1:CH2 to the double bonds of substrates 1a-d.The carbene, generated by photolysis of CH2N2, inserted into the C-H bonds of solvent and substrate, added to the substrate double bond to give products 2a-d, and attacked the oxygen or sulfur atom of substrates 1a-c to produce ylide intermediates which underwent 2,3-sigmatropic rearrangement to give products 3a-c.A preference for addition syn to the methoxy group of substrate 1a was observed when the reaction was run in pentane solution (syn-2a/anti-2a, 1.14 +/- 0.02), while a preference for formation of anti-2a was observed in diethyl ether solution (syn-2a/anti-2a, 0.92 +/- 0.03).A preference for 1:CH2 addition anti to the substrate substituent was observed for substrates 1b-d in both pentane and ether solution.The effect of the methoxy substituent was also examined in the addition of 1:CH2 to syn-7-methoxynorbornene (5b).Explanations for the substituent effects are offered based on both steric hindrance and interaction between 1:CH2 and the substituent, including formation and subsequent reaction of the ylide intermediates.
SYNTHESIS OF 3-SUBSTITUTED trans-2-OXADECALINS AND 1-SUBSTITUTED trans-2-OXAHYDRINDANES
Volynskii, N. P.,Alikhanova, O. L.
, p. 1652 - 1663 (2007/10/02)
A study was carried out of the intramolecular cyclization of trans-1-methoxymethyl-2-(1-hydroxyalkyl)cyclohexanes and trans-1-methoxymethyl-2-(2-hydroxyalkyl)cyclohexanes by the action of acid chlorides of phosphorous, sulfurous and p-toluenesulfonic acid
