Addition to alkenes and alkynes

Halogenation of alkene: undecylenic acid (a terminal alkene) with Br2; ether, 0 °C gives 10,11-dibromoundecanoic acid (the vicinal dihalide).

Carbene cyclopropanation: 3-methyl-2-buten-1-OL (a trisubstituted alkene) with CH2I2; Et2Zn gives (2,2-dimethylcyclopropyl)methanol (the cyclopropane).

HX addition: methyl acrylate (an α,β-unsaturated ester) with HBr; CH3CH2OCH2CH3 gives methyl 3-bromopropanoate (the primary alkyl bromide).

Hydrogenation: diethyl cyclohex-4-ene-1,2-dicarboxylate (a six-membered cycloalkene) with H2 (2 atm); Pt (or Pd/C) gives 1,2-diethyl 1,2-cyclohexanedicarboxylate (the saturated product).

Oxymercuration: 1-methylcyclohexene (a trisubstituted six-membered cycloalkene) with 1) Hg(OAc)2, H2O, ether; Hg0; 2) NaBH4, H2O, ether, NaOH gives 1-methylcyclohexanol (the tertiary alcohol).

Epoxidation: 1,2-dimethyl-1,4-cyclohexadiene (a tetrasubstituted six-membered cycloalkene) with mCPBA; CHCl3, Δ gives 1,6-dimethyl-7-oxabicyclo[4.1.0]hept-3-ene (the epoxide).

Halohydrin formation: crotonaldehyde (an α,β-unsaturated aldehyde) with Cl2, H2O gives 2-chloro-3-hydroxybutanal (the halohydrin).

Dihydroxylation: cyclohexene (a six-membered cycloalkene) with H2O2; HCO2H; H2O gives the 1,2-diol.

Haloetherification: (Z)-dec-4-en-1-ol (a cis-1,2-disubstituted alkene) with CH2Cl2 gives the haloether.

Hydroboration: 1-hexyne (a terminal alkyne) with 1); 2) NaOH / H2O2 gives hexanal (the anti-Markovnikov product).

Alkyne hydration: 1-ethynylcyclohexanol (a terminal alkyne) with HgO, H2SO4; H2O, 60 °C gives 1-acetylcyclohexanol (the methyl ketone).

Oxidative cleavage: di-tert-butyl tartrate (a 1,2-diol) with Pb(OAc)4; benzene (gives 2 equiv of the glyoxylate) gives tert-butyl 2-oxoacetate (the aliphatic aldehyde).

Halogenation of alkene: fumaric acid (an α,β-unsaturated acid) with Br2, H2O; Δ gives 2,3-dibromosuccinic acid (the vicinal dihalide).

Halogenation of alkene: cyclohexene (a six-membered cycloalkene) with Br2, CH3CH2OH; CCl4; −5 to −1 °C gives 1,2-dibromocyclohexane (the vicinal dihalide).

Halogenation of alkene: ethyl cinnamate (an α,β-unsaturated ester) with Br2; CCl4, 0 °C gives ethyl 2,3-dibromo-3-phenylpropanoate (the vicinal dihalide).

Carbene cyclopropanation: 3,4-dihydro-2H-pyran (an enol ether) with Cl3CCO2Et, NaOMe; pentane (dichlorocarbene from the trichloroacetate) gives 7,7-dichloro-2-oxabicyclo[4.1.0]heptane (the cyclopropane).

Halohydrin formation: [(2Z,6E)-3,7,11-trimethyldodeca-2,6,10-trienyl] acetate (a trisubstituted alkene) with NBS, (CH3)3OH; H2O, 12-25 °C gives the halohydrin.

HX addition: indene (a styrene) with HCl gives 1-chloro-2,3-dihydro-1H-indene (the benzylic alkyl chloride).

Halogenation of alkene: a trisubstituted six-membered cycloalkene with Br2, NaOAc; AcOH, ether gives the vicinal dihalide.

Epoxidation: trans-stilbene (a styrene) with peracetic acid, NaOAc; AcOH, CH2Cl2 gives the epoxide.

Halogenation of alkene: benzylideneacetone (an α,β-unsaturated ketone) with Br2, CCl4; dark gives 3,4-dibromo-4-phenyl-2-butanone (the vicinal dihalide).

Epoxidation: 1,2,3,4,5,6-hexamethylbicyclo(2,2,0)hexa-2,5-diene (a tetrasubstituted four-membered cycloalkene) with mCPBA; toluene, 0-25 °C gives the epoxide.

Dihydroxylation: cyclohexene (a six-membered cycloalkene) and methyl morpholine oxide (a cyclic ether) with OsO4 (cat.), NMO; H2O, acetone gives the 1,2-diol and 4-methylmorpholine (the diol).

Epoxidation: styrene with CHCl3, 0 °C gives styrene oxide (the epoxide).

Hydrogenation: furan with H2 (100 psi); PdO gives tetrahydrofuran (the saturated product).

Carbene cyclopropanation: cyclooctene (an eight-membered cycloalkene) with CH3Li; ether, −35 °C gives 9,9-dibromobicyclo[6.1.0]nonane (the cyclopropane).

Halogenation of alkene: oleic acid (a cis-1,2-disubstituted alkene) with Br2; ether gives the vicinal dihalide.

Carbene cyclopropanation: tert-butyl 1,2,3,4-tetrahydropyridine-1-carboxylate (an enamine) with CARBENE; 180 ºC gives the cyclopropane.

Halohydrin formation: trans-stilbene (a styrene) with NBS; H2O, DMSO gives the halohydrin.

HX addition: a 1,1-disubstituted alkene with HCl gives the secondary alkyl chloride.

HX addition: 7-methylidenedispiro[2.0.2~4~.1~3~]heptane (a 1,1-disubstituted alkene) with HBr gives 7-bromo-7-methyldispiro[2.0.24.13]heptane (the tertiary alkyl bromide).

HX addition: trans-3-hexene (a trans-1,2-disubstituted alkene) with HCl gives 3-chlorohexane (the secondary alkyl chloride).

Hydroboration: 1-methylcyclopentene (a trisubstituted five-membered cycloalkene) with BH3•SMe2; 1); 2) NaOH / H2O2 gives 2-methylcyclopentanol (the anti-Markovnikov product).

Oxymercuration: 4-pentynoic acid (a terminal alkyne) with 1); Hg(OAc)2; CH2Cl2; 2); NaBH4 gives 5-methylideneoxolan-2-one (the Markovnikov addition product).

Carbene cyclopropanation: a 1,1-disubstituted alkene with Zn/Cu; CH2I2 gives the cyclopropane.

Oxymercuration: isobutenylbenzene (a styrene) with (±) gives the ether.

Halogenation of alkene: (3aR,7aS)-1,3,3a,4,7,7a-hexahydro-2-benzofuran (a six-membered cycloalkene) with (±) gives the vicinal dihalide.

Halogenation of alkene: (E)-oct-4-ene (a trans-1,2-disubstituted alkene) with (±) gives the vicinal dihalide.

Haloetherification: 1,3-butadiene (a conjugated diene) with 38%; 62% gives (E)-1-bromo-4-[(2-methylpropan-2-yl)oxy]but-2-ene (the haloether) and the haloether.

Halogenation of alkene: 1,3-butadiene (a conjugated diene) with 100% gives trans-1,4-dibromo-2-butene (the dihalide).

HX addition: [(E)-prop-1-enyl]benzene (a styrene) with HBr gives (1-bromopropyl)benzene (the benzylic alkyl bromide).

Hydrogenation: a trisubstituted six-membered cycloalkene with H2 / PtO2; AcOH gives the saturated product.

Carbene cyclopropanation: 2,3-dimethyl-2-butene (a tetrasubstituted alkene) with CHBr3; tBuOK gives 1,1-dibromo-2,2,3,3-tetramethylcyclopropane.

Carbene cyclopropanation: a conjugated diene with CH2Cl2; Et2Zn; (1 equiv) gives the cyclopropane.

Carbene cyclopropanation: cyclohexene (a six-membered cycloalkene) with CH2I2, Zn(Cu); ether, Δ gives bicyclo(4.1.0)heptane (the cyclopropane).

Carbene cyclopropanation: 1,4-cyclohexadiene (a six-membered cycloalkene) with t-BuOK; CHCl3, 0-5 °C gives 7,7-dichlorobicyclo[4.1.0]hept-3-ene (the cyclopropane).

Hydrogenation: chalcone (an α,β-unsaturated ketone) with H2 (3 atm), PtO2; CH3CH2OAc gives dihydrochalcone (the saturated product).

Hydrogenation: (1Z,5E,9E)-cyclododeca-1,5,9-triene (a 12-membered cycloalkene) with H2NNH2, air, CuSO4; CH3CH2OH, H2O gives cyclododecene (the saturated product).

Hydrogenation: a five-membered cycloalkene with H2 (50 psi), PtO2; ether gives the saturated product.

HX addition: cyclohexene (a six-membered cycloalkene) with KI, H3PO4; 80 °C gives iodocyclohexane (the secondary alkyl iodide).

Oxymercuration: methyl acrylate (an α,β-unsaturated ester) with Hg(OAc)2; CH3OH gives the ether.

Oxymercuration: 1-pentene (a terminal alkene) with 1); 2) gives 2-pentanol (the secondary alcohol).