78426-32-1Relevant academic research and scientific papers
Synthetic studies on CP-225,917 and CP-263,114: Access to advanced tetracyclic systems by intramolecular conjugate displacement and [2,3]-wittig rearrangement
Malihi, Farzad,Clive, Derrick L. J.,Chang, Che-Chien,Minaruzzaman
, p. 996 - 1013 (2013/04/10)
An advanced intermediate related to the structures of CP-225,917 and CP-263,114 was constructed by a sequence based on the use of Grob-like fragmentation, intramolecular conjugate displacement, and [2,3]-Wittig rearrangement. A variant of the [2,3]-Wittig rearrangement was developed.
Scandium(III) triflate catalyzed synthesis of primary homoallylic alcohols via carbonyl-ene reaction
Sultana, Sabera,Bondalapati, Somasekhar,Indukuri, Kiran,Gogoi, Paramartha,Saha, Pipas,Saikia, Anil K.
supporting information, p. 1576 - 1578 (2013/03/28)
Scandium trifluoromethanesulfonate can efficiently catalyze the formation of homoallylic alcohols from olefins and paraformaldehyde in good yields.
[2,3]-Wittig rearrangement by a chlorine-lithium exchange
Maciá, Beatriz,Gómez, Cecilia,Yus, Miguel
, p. 6101 - 6104 (2007/10/03)
The reaction of different allylic chloromethyl ethers 1 with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (2.5 mol %) in THF at 0°C for 1 h gives, after hydrolysis with water, the expected alcohols 2 resulting from a [2,3]-Wittig rearrangement, in an exclusive manner. The same process can also be applied to the corresponding [1,2]-Wittig rearrangement, as it is exemplified for benzyl chloromethyl ether.
Formaldehyde Encapsulated in Zeolite: A Long-Lived, Highly Activated One-Carbon Electrophile to Carbonyl-Ene Reactions
Okachi, Takahiro,Onaka, Makoto
, p. 2306 - 2307 (2007/10/03)
Gaseous formaldehyde is extremely unstable and readily undergoes self-polymerization to a solid paraformaldehyde or disproportionation to methanol and formic acid in the presence of moisture. We disclose a simple method to stably store such a labile formaldehyde as a monomer in a nanoporous faujasite zeolite at 5 °C for at least 50 days without self-polymerization or disproportionation. The greater stability of formaldehyde encapsulated in zeolite was confirmed by 13C MAS NMR spectroscopy. Formaldehyde was not only stabilized within the zeolite cages but functioned as a powerful electrophile toward various olefins. Zeolite-encapsulated formaldehyde was proved to be a stable but highly reactive C1 reagent. Copyright
Isocyclic allylsilanes: An efficient one-pot synthesis of allylic hydroxymethyl methylenecycloalkane building blocks by a controlled H-ene/protodesilylation sequence using two different Lewis acids
Monti, Honore,Feraud, Michel
, p. 1721 - 1728 (2007/10/03)
An efficient one-pot synthesis of useful allylic hydroxymethyl methylenecycloalkane building blocks was achieved by a controlled H-ene/protodesilylation sequence using two different Lewis acids (Me2AlCl/SnCl4) and starting from readily available isocyclic allylsilanes.
Stabilization of reactive aldehydes by complexation with methylaluminum bis(2,6-diphenylphenoxide) and their synthetic application
Maruoka, Keiji,Concepcion, Arnel B.,Murase, Noriaki,Oishi, Masataka,Hirayama, Naoki,Yamamoto, Hisashi
, p. 3943 - 3949 (2007/10/02)
Reactive aldehydes such as formaldehyde and α-chloro aldehydes can be successfully generated by treatment of readily available trioxane and α-chloro aldehyde trimers, respectively, with methylaluminum bis(2,6-diphenylphenoxide) (MAPH), and stabilized as their 1:1 coordination complexes with MAPH. The resulting CH2=O·MAPH complex reacts with a variety of olefins to furnish ene-reaction products with excellent regio- and stereoselectivities. In addition, this complex as well as α-chloro aldehyde-M APH complexes can be utilized as a stable source of gaseous formaldehyde and reactive α-chloro aldehydes, respectively, for the nucleophilic addition of various carbanions (organometallics, enolates, etc.). Formation of reactive aldehyde-MAPH complexes is firmly confirmed by 1H NMR spectroscopy. A space-filling model of aldehyde-M APH complexes implies that formaldehyde and α-chloro aldehydes coordinated with MAPH may be electronically stabilized by two parallel phenyl groups of aluminum ligands.
Synthesis with organoboranes V. Hydroxymethylation and formylation of cycloalkenes via allylic organopotassium and organoboron compounds
Zaidlewicz, Marek
, p. 103 - 107 (2007/10/02)
Allylic hydroxymethylation of cyclohexene and cyclooctene was achieved by metallation with trimethylsilylmethylpotassium followed by the reaction with formaldehyde. 1-Methylcycloalkenes were transformed into 2-methylenecycloalkane-1-methanols by the reaction of formaldehyde with allylic diethylboranes derived from these olefins via metallation-transmetallation.Conjugated cycloalkenecarboxaldehydes were obtained by oxidation of the hydroxymethylation products.
DIMETHYLALUMINUM CHLORIDE CATALYZED ENE REACTIONS OF ALDEHYDES.
Snider,Rodini,Kirk,Cordova
, p. 555 - 563 (2007/10/02)
Dimethylaluminum chloride, which is a mild Lewis acid and a proton scavenger, catalyzes the ene reactions of aliphatic and aromatic aldehydes with alkenes containing a disubstituted vinylic carbon. Proton-initiated rearrangements do not occur, since the alcohol-Lewis acid complex formed in the ene reaction reacts rapidly to give methane and a nonacidic aluminum alkoxide. Formaldehyde and excess Me//2AlCl give good yields of ene adducts with all types of alkenes. With 1 equiv of Me//2AlCl, formaldehyde and mono- and 1,2-disubstituted alkenes give gamma -chloro alcohols resulting from cis addition of chlorine and hydroxymethyl groups to the double bond. This work is pertinent to the synthesis of alcohols.
