Orgo Test 3 (past reactions)

Name the stabilized, un-stabilized, and non-selective phosphorous ylids. What alkene stereoisomers do they produce?

Reagents and product for alkene reduction.

Reagents: H2, Pd

Product: alkane

Reagent’s for alkyne reduction to an alkane.

H2, Pd

Reagents for cis alkyne reduction.

Lindlar’s catalyst, H2

Reagents for trans alkyne reduction.

NH3, Li

Reagents and product for aldehyde reduction.

Reagents: NaBH4, LiAlH4, LiBH4

Product: primary alcohol

Reagents and product for ketone reduction.

Reagents: LiAlH4, LiBH4, and NaBH4

Product: secondary alcohol

Reagents and product for ester reduction.

Reagents: LiAlH4, LiBH4

Product: primary alcohol

Reagents and product for carb. acid reduction.

Reagents: LiAlH4, BH3

Product: primary alcohol

Reagents and product for amide reduction.

Reagents: LiAlH3, BH3

Product: amine

Reactants, reagents, and products of reductive animation.

Reactants: ketone/aldehyde, amine

Reagents: LiAlH4, LiBH4, BH3, NaBH4, or NaCNBH3

Product: amine

Primary alcohol to aldehyde reagents.

Weak oxidizing agent (PCC, DMP, PDC, TPAP, NMO) w/ CH2Cl2

Reagents for primary alcohol to carboxylic acid.

Strong oxidizing agent (H2CrO4, KMnO4)

Reagents and product of secondary alcohol oxidation

Reagents: oxidizing agent, typically H2CrO4, KMnO4 can also be DMSO (via Swern oxi.) or Dess-Martin

Product: ketone

Reagents for alkene oxidation to aldehyde/ketone

O3, Me2S

Reagents for alkene to carb. acid

O3, H2O2 or KMnO4

Reagents for alkene to diol

MnO4 or OsO4

Reagents and product of epoxide opening

Reagent: nucleophile

Product: alcohol, diol if nucleophile is water

Reagent for synthesis of an aldehyde from an ester.

DIBAL

Reagent for epoxidation of alkene

m-CPBA

Reactants and reagents for E2 to form an alkene.

Reactants: alkyl halide or alcohol

Reagents: base (alkyl halide) or acid (alcohol)

What do benzyl ethers protect? How are they installed? How are they removed?

They protect alcohols. They are installed through NaH and BnBr. They are removed through H2, Pd/C, and HBr.

Reagents for carboxylic acid to acid chloride.

SOCl2 or PCl5

Reagent for acid chloride to acid anhydride.

carboxylic acid

Alkene Hydroboration/Oxidation reagents and products

Reagents: 1) BH3, B2H6 2) oxidant (H2O2) in the presence of base (NaOH, KOH)

Product: alcohol

Reagents and products of alkene oxymercuration

Reagents: 1) mercury salt (Hg(OAc)2) and water) 2) NaBH4

Product: alcohol

Reagents for alkylation of 1,3-dicrbonyl

1) LDA 2) alkyl halide

Reagents for alkyne alkylation

Base (NaNH2) & alkyl bromide OR BuLi & alkyl chloride

Reactants, reagents, and products of Diels–Alder Reaction​

Reactants: diene (conjuagted, cis confirmation) , pi bond (dienophile)

Reagents: heat

Product: six-membered ring w/ one pi bond

Reactants and reagents for friedel-craft alkylation.

Reactants: benzene, alkyl halide

Reagents: Lewis acid (AlCl3)

Reactants and reagents for friedel-craft acylation.

Reactant: benzene, acyl group

Reagents: Lewis acid (AlCl3)

Ractants, reagents, and products of Vilsmeier–Haack Formylation

Raeactants: aromatic ring or pyrrole and an amide

Reagetns: POCl3, DMF

Products: aryl aldehyde

Reactants, reagents, and products of Weinreb Ketone Synthesis

Reactants: N-methoxy-N-methyl amide

Reagetns: organomagensium or organolithium reagents, acid

Product: ketone

Order of carbonyl reactivity

Give a list of benzene functional groups from least reactive to most reactive. State if they are meta-, ortho-, or para-directing activators/deactivators.

Reactants, reagents, and products for nitration reaction.

Reactants: benzene, nitric acid

Reagens: H2SO4

Products: nitrobenzene

Reactants and reagent for ortholithiation

Reactant: mono-substituted benzene

Reagent: Bu-Li

What are the typical components of a nucleophilic aromatic substitution?

What nucleophiles produce steric selectivity in epoxide opening?

Basic nucleophiles attack the less substituted carbon. Acidic nucleophiles attack the more substituted carbon.

Reactants, reagents, and products of markinov’s reaction. Describe selectivity. What us an exception to rule?

Reactants: alkene

Reagents: HX

Product: alkyl halide

The halide will attach to the most substituted carbon, unless Borane is being added, in which case BH2 will be added to the least substituted carbon.

Corey−Chaykovsky Epoxidation reactants, reagents, and products.

Reactants: aldehydes/ketones

Reagent: sulfonium or sulfoxonium ylid

Product: epoxide

Corey−Chaykovsky cycloproponation reactants, reagents, and products.

Reactants: 1,3- conjuagted keton/aldehyde

Reagent: sulfoxonium ylid

Product: cyclopropane

Julia olefination reactants, reagents, and products.

Reactants: phenyl sulfone

Reagents: 1) BuLi 2) aldehyde/ketone 3) acetic anhydride

Product: trans alkene

Wittig reactants, reagents, and products.

Reactants: ketone/aldehyde

Reagents: phosphonium ylid

Product: cis/trans alkene depending on ylid