Fully substituted olefin generation via metathesis is presented. Catalyst development, optimization of reaction conditions and substrate screening are included. In addition, asymmetric alkene metathesis, the cross metathesis reaction for this transformation and its application in natural products will be discussed.

The Ni-catalyzed coupling of allyl chlorides and enynes has been developed; the cyclization of enynes was triggered by the addition of pi-allylnickel species to the alkyne part, followed by the incorporation of the alkene part.

Fe(BF(4))(2)·6H(2)O with pyridine-2,6-dicarboxylic acid and PhIO can efficiently catalyze the regioselective oxidation of terminal alkene derivatives to aldehydes under mild and benign reaction conditions.

2,2-Disubstituted cyclic 1,3-diketones containing a tethered electron-deficient alkene undergo chiral phosphoric acid-catalyzed desymmetrizing Michael cyclizations to give bridged bicyclic products in high enantioselectivities. Both bicyclo[3.2.1]octanes and bicyclo[3.3.1]nonanes are accessible using this methodology.

Semisynthesis studies starting from (11Z)-1',2'-didehydrostemofoline (4) indicated that the known Stemona alkaloid stemoburkilline is the Z-isomer and not the E-isomer as initially reported. The semisynthesis involved conversion of (11Z)-1',2'-didehydrostemofoline (4) to 11(S),12(S)-dihydrostemofoline (3) followed by a stereoselective base-catalyzed ring-opening reaction to give (Z)-stemoburkil...

Hydrocarbons were extracted from the surface of the cuticle and from the hemolymph of adult female gypsy moths. GC and GC/MS analysis indicated that the cuticular hydrocarbons with chain lengths >21 carbons were the same as those found in the hemolymph. These consisted of mostly saturated straight chain hydrocarbons with heptacosane the major component. Methyl branched hydrocarbons were also id...

The pheromone biosynthetic pathway for production of the sex pheromone disparlure, 2-methyl-7R,8S-epoxy-octadecane, was determined for the gypsy moth. Each step in the pathway was followed by using deuterium-labeled compounds that could be identified by using GCMS. This approach provides unequivocal determination of specific reactions in the pathway. It was shown that the alkene precursor, 2-me...

Biological production of terminal alkenes has garnered a significant interest due to their industrial applications such as lubricants, detergents and fuels. Here, we engineered the yeast Saccharomyces cerevisiae to produce terminal alkenes via a one-step fatty acid decarboxylation pathway and improved the alkene production using combinatorial engineering strategies. In brief, we first character...

10 MH+ ions from sec-alkyl m-dimethylamino ethers have been studied by MS/MS using chemical ionization (CI) and electrospray ionization (ESI). Collisionally activated dissociation (CAD) of MH+ from the vicinally perdeuterated 3-hexyl ether, CH3CD2CHOArCD2CH2CH3, shows that alkene expulsion is >96% regioselective, yielding m/z 139 and m/z 124 fragment ions. The fact that alkene elimination is no...

The kinetics of the decomposition of 4-methyl-1-pentyl radicals have been studied from 927-1068 K at pressures of 1.78-2.44 bar using a single pulse shock tube with product analysis. The reactant radicals were formed from the thermal C-I bond fission of 1-iodo-4-methylpentane, and a radical inhibitor was used to prevent interference from bimolecular reactions. 4-Methyl-1-pentyl radicals undergo...