18516-37-5Relevant articles and documents
Synthesis of α-Tertiary Amine Derivatives by Intermolecular Hydroamination of Unfunctionalized Alkenes with Sulfamates under Trifluoromethanesulfonic Acid Catalysis
Fei, Jun,Wang, Zhen,Cai, Zheren,Sun, Hao,Cheng, Xu
supporting information, p. 4063 - 4068 (2016/01/25)
An efficient and mild trifluoromethanesulfonic acid-catalyzed hydroamination of unfunctionalized alkenes to afford α-tertiary amine derivatives at temperatures as low as room temperature is reported. 2,2,2-Trifluoroethyl sulfamate was found to be the optimal nitrogen source because its good solubility in both organic solvents and water facilitated both conversion and purification. The reaction conditions were compatible with a variety of substrate functional groups and afforded moderate to good yields. The desired amine compounds could be obtained easily by means of a mild, one-pot, redox-neutral deprotection procedure. Caryolane amine was synthesized with excellent chemo- and regioselectivities by means of a cascade hydroamination reaction of β-caryophyllene.
Simple, chemoselective, catalytic olefin isomerization
Crossley, Steven W. M.,Barabé, Francis,Shenvi, Ryan A.
supporting information, p. 16788 - 16791 (2015/01/09)
Catalytic amounts of Co(SaltBu,tBu)Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.
Cylindrocyclophane biosynthesis involves functionalization of an unactivated carbon center
Nakamura, Hitomi,Hamer, Hilary A.,Sirasani, Gopal,Balskus, Emily P.
supporting information, p. 18518 - 18521 (2013/01/15)
The cylindrocyclophanes are a family of natural products that share a remarkable paracyclophane carbon scaffold. Using genome sequencing and bioinformatic analyses, we have discovered a biosynthetic gene cluster involved in the assembly of cylindrocyclophane F. Through a combination of in vitro enzyme characterization and feeding studies, we confirm the connection between this gene cluster and cylindrocyclophane production, elucidate the chemical events involved in initiating and terminating an unusual type I polyketide synthase assembly line, and discover that macrocycle assembly involves functionalization of an unactivated carbon center.
Iron thiolate complexes: Efficient catalysts for coupling alkenyl halides with alkyl grignard reagents
Cahiez, Gerard,Gager, Olivier,Buendia, Julien,Patinote, Cindy
supporting information; experimental part, p. 5860 - 5863 (2012/07/01)
Ironing out the kinks: Efficient new catalytic systems based on iron thiolates are described for the iron-catalyzed cross-coupling of alkyl Grignard reagents with alkenyl halides (see scheme). The reaction is highly chemo- and stereoselective. With this new procedure, the use of N-methylpyrrolidone as a co-solvent is no longer required. Copyright
Fritsch-Buttenberg-Wiechell rearrangement to alkynes from gem-dihaloalkenes with lanthanum metal
Umeda, Rui,Yuasa, Takumi,Anahara, Namika,Nishiyama, Yutaka
supporting information; experimental part, p. 1916 - 1919 (2011/05/14)
The first example of the FBW rearrangement using of lanthanum metal and a catalytic amount of iodine was disclosed. When gem-diiodo- and gem-dibromoalkenes were treated with lanthanum metal in the presence of a catalytic amount of iodine, the reductive dehalogenation of these compounds smoothly proceeded to produce the corresponding alkynes in moderate to good yields.
Terminal olefins from aldehydes through enol triflate reduction
Pandey, Sushil K.,Greene, Andrew E.,Poisson, Jean-Francois
, p. 7769 - 7770 (2008/02/12)
(Chemical Equation Presented) The transformation of aldehydes into terminal olefins through reduction of the corresponding enol triflates is described. The method is effective with both linear and α-branched aldehydes.
Zinc-mediated synthesis of tertiary alkyl selenides from tertiary alkyl halides
Krief, Alain,Derock, Michel,Lacroix, Damien
, p. 2832 - 2834 (2007/10/03)
Diorganyl selenides are efficiently synthesized from tertiary alkyl halides, selenols or selenolates and zinc dibromide as well as from diselenides in the presence of zinc. Georg Thieme Verlag Stuttgart.
PROCESS FOR PRODUCING PHENYL-ALKANES USING OLEFIN ISOMERIZATION AND PARAFFIN RECYCLE
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Page/Page column 17-19, (2008/06/13)
A process for producing phenyl-alkanes by paraffin dehydrogenation followed by olefin isomerization and then by alkylation of a phenyl compound by a lightly branched olefin is disclosed. An effluent of the alkylation section comprises paraffins that are recycled to the dehydrogenation step. A process that sulfonates phenyl-alkanes having lightly branched aliphatic alkyl groups to produce modified alkylbenzene sulfonates is also disclosed. In addition, the compositions produced by these processes, which can comprise detergents, lubricants, and lubricant additives, are disclosed.
Scandium trifluoromethanesulfonate as an extremely active Lewis acid catalyst in acylation of alcohols with acid anhydrides and mixed anhydrides
Ishihara, Kazuaki,Kubota, Manabu,Kurihara, Hideki,Yamamoto, Hisashi
, p. 4560 - 4567 (2007/10/03)
Scandium trifluoromethanesulfonate (triflate), which is commercially available, is a practical and useful Lewis acid catalyst for acylation of alcohols with acid anhydrides or the esterification of alcohols by carboxylic acids in the presence of p-nitrobenzoic anhydrides. The remarkably high catalytic activity of scandium triflate can be used for assisting the acylation by acid anhydrides of not only primary alcohols but also sterically-hindered secondary or tertiary alcohols. The method presented is especially effective for selective macrolactonization of ω-hydroxy carboxylic acids.
Unusual Directive Effects in the Hydroboration of β,β-Disubstituted Enamines. Conversion of α-Substituted Aldehydes to the Corresponding Alkenes and β-Amino Alcohols
Singaram, Bakthan,Goralski, Christian T.,Fisher, Gary B.
, p. 5691 - 5696 (2007/10/02)
A comprehensive study of the conversion of β,β-disubstituted enamines into the corresponding alkenes and β-amino alcohols by hydroboration-elimination and hydroboration-oxidation, respectively, has been carried out.The amine moiety of β,β-disubstituted enamines was found to exert a decisive influence on the regioselectivity of the hydroboration reaction involving borane methyl sulfide (BMS).Thus, in the hydroboration of morpholino and piperidino enamines, the boron atom is initially placed predominantly in the α-position.Conversely, the pyrrolidino enamines direct the boron atom exclusively to the β-position.Three oxidizing agents, trimethylamine N-oxide, sodium perborate, and 30 percent hydrogen peroxide-solid sodium hydroxide, were tried in order to optimize the oxidation of the intermediate organoborane derivatives to the corresponding amino alcohols.Our results clearly indicated that 30 percent hydrogen peroxide-solid sodium hydroxide is best suited for this transformation.The yield of amino alcohol ranged from good to essentially quantitative.Enamines derived from β-aryl aldehydes, upon hydroboration with BMS followed by methanolysis and oxidation with neutral hydrogen peroxide, gave the corresponding 1,1-disubstituted alkenes.Contrary to the regioselectivity observed in the hydroboration reactions involving BMS, the hydroboration of β,β-disubstituted enamines using 9-borabicyclononane (9-BBN) gave the trialkylborane intermediates in which the boron atom was placed exclusively at the β-position regardless of the amine moiety of the enamine.These trialkylborane derivatives were very stable and did not undergo the usual elimination reaction with either methanol or sodium hydroxide.However, on thermal decomposition, these afforded the corresponding 1,1-disubstituted alkenes in high yields.
