Orgo I, Ch 8,9,10 Reactions

Sn2

strong nucleophile, polar aprotic; concerted; 100% inversion of chiral center; nuc replaces leaving group

Sn1

weak nuc/base, polar aprotic; stepwise; racemic mixture; nuc replaces leaving group

E2

strong base, polar protic; concerted; Zaisev’s product unless the base is sterically hindered; base takes anti-periplanar proton, kicks off leaving group, forms alkene

E1

weak base/nuc, polar protic; stepwise; always produces Zaitsev product; LG departs, carbocation intermediate forms (rearrangement), base takes proton, forms alkene

Alkene + HX

Hydrohalogenation; Markovnikov addition of halogen (X) and an H across alkene

Alkene + HBr, ROOR

Hydrohalogenation; non-Markovnikov addition of Br and H across an alkene in the presence of a reducing agent

Alkene + H3O⁺ (conc. acid, H2O)

Acid-catalyzed Hydration; Markovnikov addition of water as H and OH across an alkene

Alkene + 1) Hg(OAc)2, H2O 2) NaBH4

Oxymercuration, Demercuration; adding H2O across an alkene by Hg(AOc)2 forms a mercurinium intermediate which is demercurated by NaBH4 to add OH and H across the bond (Markovnikov)

Alkene + 1) BH3, H2O 2) H2O2, NaOH

Hydroboration-oxidation; anti-Markovnikov addition of OH and H across an alkene; concerted; syn addition (product + enantiomer)

Alkene + H2, Pt

Hydrogenation (metal catalyzed); addition of H2 across an alkene in the presence of a metal catalyst; syn addition (product + enantiomer)

Alkene + Br2

Bromination; addition of Br2 across an alkene; anti addition where the second bromine addition is by Sn2 (backside attack) (product + enantiomer)

Alkene + X2, H2O

Halohydrin formation; addition of Br and OH across an alkene; OH is added anti-Markovnikov (product + enantiomer)

Alkene + RCO3H

Anti Dehydroxylation; adding OH and OH across an alkene; anti addition (product + enantiomer)

Alkene + OsO4, NaSO4

Syn Dehydroxylation; OsO4 added (syn) across the alkene and is treated with NaSO4 to make a diol

Alkene + O3, DMS

Ozonolysis; O3 cleaves pi bond with treated with a reducing agent (cut double bond in half, add =O)

alkene + NBS/ light, CCl₄

allylic bromination to make an alkyl halide

alcohol + HX/ ether

alkyl halide formation (S_N2)

(primary/ secondary) alcohol + SOCl₂/ pyridine

alkyl halide (Cl for OH)

(primary/ secondary) alcohols + PBr₃ / ether

alkyl halide (Br for OH)

(primary/ secondary) alcohol + HF/ pyridine

alkyl halide (F for OH)

RX + Mg/ ether

(Grignard reagent formation) R-Mg-X

RX + 2Li/pentane

(Gilman reagent formation) R-Li + Li-X

2R-Li + CuI → R-Cu-R + LiX

Diorganocopper Reaction

R₂CuLi + R’-X → (in ether) → R-R’ + RCu + LiX

alkyne + HX (xs)

(Hydrohalogenation) Markovnikov addition of 2 equivalents of X

alkane + NaNH₂ (xs) / H₂O

Elimination (of geminal or vicinal) alkyl halide to make a terminal alkyne (E2 twice)

alkyne + HgSO₄ / H₂SO₄, H₂O

(acid-catalyzed hydration) Markovnikov addition of OH to the alkyne to make an enol which, under acidic conditions, tautomerizes to a ketone

alkyne + R₂BH / H₂O₂, NaOH

(hydroboration, oxidation) Markovnikov addition of OH to the alkyne to make an enol which, under basic conditions, deprotonates to make an enolate anion and tautomerizes to becomes an aldehyde

alkyne + X₂ (1 equiv.)/ CCl₄

(Halogenation) addition of X-X across the triple bond to make an alkene

alkyne + X₂ (xs) / CCl₄

(Halogenation) addition of 2 equivalents of X-X across the triple bond to make an alkane

alkyne + O₃ / H₂O

(Ozonolysis) Cleavage of a triple bond to make a carboxylic acid and a carbon dioxide

alkyne + NaNH₂ / RX

(Alkylation) aldehyde is deprotonated by NH₂^- to form an acetylide anion which reacts wit RCH₂Br to add an R group to the less substituted side of the alkyne

(alkylated) alkyne + Na/ NH₃ (l)

reduction to a trans alkene

(alkylated) alkyne + H₂/ Pd

reduction to an alkane

(alkylated) alkyne + H₂/ Lindlar’s Catalyst

reduction to a cis alkene

Friedel-Crafts Alkylation (benzene ring + R-Cl/ AlCl₃ → substituted benzene)

a strong electrophile is substituted for a hydrogen atom on an aromatic (benzene) ring; benzene ring + strong electrophile → carbocation intermediation deprotonated by the conjugate base of the electrophile to restore aromaticity (back to sp2)

Friedel-Crafts Acylation (benzene + acyl/ AlCl₃ → acyl-substituted benzene)

an acyl group is substituted for a hydrogen atom on an aromatic (benzene) ring; benzene ring + strong electrophile → carbocation intermediation deprotonated by the conjugate base of the electrophile to restore aromaticity (back to sp2)