2- Methyl-2-heptene, alkylation

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

The metabolism of oleftnic or acetylenic substances to electrophilic metabolites is greatly reduced when the oleftnic or acetylenic moieties are not terminal, or are terminal but contain alkyl substituents on the allylic and propargylic positions. 1-Heptene, for example, is bioactivated to electrophilic metabolites whereas 3-hexene, 2-methyl-l-hepteneand3,3-dimethyl-l-hexenearenot [36,37]. Similarly, 1-decyneismetabolizedto electrophilic metabolites whereas 3- and 5-decynes are essentially not [36, 37]. 

CIC The flavour of freshly roasted filberts, is a balanced composition of alkyl pyrazines and aldehydes, derived from the Maillard reaction in combination with 4-methyl-5-hepten-2-one. 

Naphthalene dioxygenase from P. putida strain FI is able to oxidize a number of halogenated ethenes, propenes, and butenes, and cis-2-heptene and cis-2-octene (Lange and Wackett 1997). Alkenes with halogen and methyl substituents at double bonds form allyl alcohols, whereas those with only alkyl or chloromethyl groups form diols. 

Various terminal alkenes reacted smoothly with 2-picoline under the same reaction conditions (Table 5.9). 1-Heptene and 1-octene could afford the expected branched products in high yields (92%) and enantioselectivity (93 7 er) (entries 1 and 2). In addition, alkenes bearing bulky substituents in close proximity to the C—C double bond (such as 4-methyl-l-pentene, allylcy-clohexane and allyltrimethylsilane) were also good alkylation agents, giving the corresponding branched alkylation products 190 in 80-95% yields and high enantioselectivity (up to 91 9 er, entries 3-5). 

The relative rates of [Mo(CO)6]-catalyzed epoxidation of olefins by erf-butyl hydroperoxide in benzene were found to be in the order allyl chloride (0.1) 1-octene (1.0) < styrene (1.3) < 2-methyl-l-heptene (9) < cyclohexene (13) < cis-2-octene (14), norbornene (14) < 2-methyl-2-heptene (75). Thus, electron donation in the form of alkyl groups about the double bond accelerates the reaction rate whereas electron withdrawal tends to retard it [379]. 

Tri(2-ethylhexyl)borane forms a rather complicated mixture of boron heterocyclics that has not yet been resolved however, the major products appear to contain six-membered rings. There are three different chains outside of the rings 2-ethyl-1-hexyl, 3-methyl-l-heptyl, and 5-methyl-l-heptyl (most common). Alkyl groups having the boron on a central carbon normally do not appear. Olefins formed consist almost entirely of 3-methyl-3-heptene and 3-methyl-2-heptene. 

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