Amines => alkenes

For the preparation of enamines or imines from ketones, see Section 356 (Amine-Alkene). 0 1. CFsSOsSiMes, MeCN S... 

Although there are other convenient procedures for the conversion of sulphides into sulphoxides and sulphones, the phase-transfer catalysed reaction using Oxone has the advantage that the oxidation can be conducted in the presence of other readily oxidized groups, such as amines, alkenes, and hydroxyl groups, and acid-labile groups, such as esters and carbamates [6, 7], Hydrolysis of very acid-labile groups, such as ketals, can result in production of the keto sulphone. 

Various acetylenes having functional groups such as halide, alcohol, ether, amine, alkene and nitrile, are tolerated in the reaction. An asymmetric (2+2+2) cydoaddition of a,03-diynes with alkyne was achieved by a [IrCl(cod)]2 catalyst combined with a chiral phosphine ligand such as MeDUPHOS and EtDUPHOS, and gave axially chiral aromatic compounds [20]. 

The root name is based on the longest continuous chain of carbon atoms bearing the carhoxyl group. The -e is replaced by -oic acid. The chain is numbered starting with the carhoxyl carbon atom. The carboxyl group takes priority over any other functional groups as follows carboxylic acid > ester > amide > nitrile > aldehyde > ketone > alcohol > amine > alkene > alkyne. 

Reactions of Pt(O,0-MeCOCHCOMe)(MeCOCH2COMe)X (X = Cl, Br) with a wide variety of donors, including phosphines, arsines, amines, alkenes, diamines, etc. have been examined. In all cases the coordinated neutral acetylacetone is displaced. When monodentate ligands, L, are employed, products are of the type Pt(0,0-MeCOCHCOMe)XL. Bidentate ligands, LL, yield Pt(C-MeCOCHCOMe)X(LL) and bridging alkenes form PtCl(0,0-MeCOCHCOMe) (dialkene).494... 

Palladium chemistry has been used in the synthesis of tetrahydroisoquinolines. Different combinations of iodoaryl-amine-alkene can be used in these multicomponent reactions. For example, the metal-mediated o-alkylated/alkenyl-ation and intramolecular aza-Michael reaction (Scheme 109) give moderate yields of heterocycle <2004TL6903>, whereas the palladium-catalyzed allene insertion-nucleophilic incorporation-Michael addition cascade (Equation 172) produces good yields of tetrahydroisoquinolines in 15 examples <2003TL7445> with further examples producing tetrahydroquinolines (Scheme 110) <2000TL7125>. 

Imines can be saturated in preference to the hydrogenation of aldehydes, ketones or nitriles and the hydrogenolysis of benzyl ethers and amines. Alkenes, alkynes and nitro groups are, however, usually hydrogenated in preference to an imine. 

A. J. Bailey, W. P. Griffith, B. C. Parkin, Heteropolyperoxo- and isopolyperoxo-tungstates and -molybdates as catalysts for the oxidation of tertiary amines, alkenes and alcohols, J. Chem. Soc., Dalton Trans. 11 (1995) 1833. 

This section contains alkylations of ketones and protected ketones, ketone transpositions and annulations, ring expansions and ring openings, and dimerizations. Conjugate reductions and Michael alkylations of enone are listed in Section 74 (Alkyls, Methylenes, and Aryls from Alkenes). For the preparation of enamines or imines from ketones, see Section 356 (Amine-Alkene). 

Even more than in the case of aromatic cyano compounds, carbonyl compounds such as enones [11], ketones [12] or imides [13] usually act as electron-accepting partners in the presence of amines. Alkenes or alkylarenes are also accepting partners in the presence of amines [14]. The coupling products are derived from an initial electron transfer followed by hydrogen atom transfer. Depending on the nature of the amine, either a CH (Scheme 5, eq 1) or an NH bond (Scheme 6, eq 2) intervene in the hydrogen atom transfer. 

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