Organic Chemistry 2 Final Exam Review

H2 (excess), Pd-c

reduces c=o to alcohols

reduces alkenes to alkanes

2 H2, Pd-c

reduced alkynes to alkanes

H2 (1 equiv), Pd-c

ONLY reduces alkenes to alkanes

1) LiAlH4 (LAH)

2) H2O

reduces everything except alkenes

reduces aldehydes to alcohols

reduces ketones to alcohols

reduces acid chlorides and esters to alcohols

reduces carboxylic acids to alcohols

reduces amides to amines

reduced alkyl halides(RX) to alkanes(RH)

opens epoxides at less substituted carbon (reduces epoxides to alcohols)

NaBH4, CH3OH

does not reduce alkenes to alkanes

ONLY reduced aldehydes and ketones to alcohols

very selective

Witting Reagents (Ph3P=CR2)

adds carbon-carbon double bond

selective to just aldehydes and ketones

converts c=o to c=c

H2O, H+ or -OH, delta

-turns CN to carboxylic acids

NaCN, HCl

adds CN as a nucleophile to a ketone or aldehyde to give a CN and an alcohol

does Sn2 nucleophilic attack

1) R”2CuLi 2)H2O (organocupurates)

does not react with ketones, aldehydes, or esters

reacts with acid chlorides to give a ketone product

reacts with alpha-beta unsaturated ketones at the beta carbon giving 1,4 addition

1) DIBAL-H 2)H2O

selective reducing agent

reduces acid chlorides and esters down to aldehydes

no rxn with carboxylic acids

1)R”MgBr 2)H2O (grinard)

reacts with aldehydes and ketones as Nu, creating an alcohol and adding carbons

reacts with acid chlorides and esters to give alcohols (2 equivs will give tertiary alcohols)

react with alpha-beta unsaturated ketones at the carbonyl carbon, giving 1,2 addition

1)R”Li 2)H2O (organolithiums)

-act as nucleophile with ketones and aldehydes, affording an alcohol and adding carbons

-turns acid chlorides and esters to alcohols and adds a carbon chain ( 2 equivs would give a tertiary alcohol)

reacts with alpha-beta unsaturated ketones at the carbonyl carbon to give 1,2 addition

Ag2O, NH4OH (tollens reagent)

-selective for turning aldehydes into carboxylic acids

CrO3, H2SO4, H2O (Jones)

-turns primary alcohols into carboxylic acids

-turns secondary alcohols into ketones

-turns aldehydes into carboxylic acids

*know mech for secondary alcohol to ketone

*know mech for primary alcohol to carboxylic acid (get to aldehyde then use chapter 18 to get to a hydrate then react with chromate again to get carboxylic acid)

acetone

acetophenone

benzophenone

formyl substituent

acetyl substituent

benzyl (Bz) substituent

formaldehyde

acetaldehyde

propionaldehyde

butyraldehyde

valeraldehyde

caproaldehyde

benzaldehyde

1) BH3 (R2BH) 2) H2O2, -OH

react with terminal alkynes to afford an aldehyde

H2O, H2SO4, HgSO4

react with terminal alkynes to afford a ketone

TBS-Cl, base

protecting group for OH, turns OH to OTBS

TBAF

deprotecting step for OH, turns OTBS back to OH

1) RNH2, mild acid 2)loss of H2O

reaction of primary amines to form an imine product

The intermediate is carbinolamine

this is reversible

*know mech

1) R2NH, mild acid 2) loss of H2O

reaction of secondary amines to form enamines

reversible reaction

intermediate is carbinoalmine

*know mech

H3O+ or H2O, H+

-does hydrolysis of imines back to a ketone/aldehyde and primary amine or enamines back to an aldehyde/ketone and secondary amine

-does hydrolysis of acetals back into a ketone/aldehyde and an alcohol (this process can also use H2SO4 and H2O)

H2O, H+ or -OH

-addition of H2O (hydration reaction)

-makes a gem-diol (hydrate) from a ketone or aldehyde

-can occur in basic or acidic condition

*Know both basic and acidic mech

1st step in basic conditions with hydration

nu attack at carbonyl

1st step in acidic conditions of hydration

Acid protonates the carbonyl oxygen

2 eq of an alcohol (or a diol) and H+ (usually in form of TsOH)

-addition of alcohol to form an acetal from a ketone or aldehyde

-an acetal is a molecule with a R group, a group that is a H or a R, and two OR groups

-removal of water or addition of excess alcohol drives this reaction to from the products

one equivalent of an alcohol with TsOH

-forms a hemiacetal from an aldehyde or ketone (very unstable)

-cycle hemiacetals that from 5 or 6 membered rings tho are very stable

HOCH2CH2OH and H+

acetals as protecting groups (turn ketones and aldehydes into an acetal to protect them from the desired reaction)

H+ and H2O

deprotecting step of acetals, turn them back into their OG aldehyde or ketone

Na, NH3

reduced alkynes to trans alkenes

H2, lindlar’s catalyst

reduced alkynes to cis alkenes

mCPBA or RCO3H

makes an epoxide from an alkene

*know this mech

1)mCPBA or RCO3H 2) H2O or -OH

anti-dihydroxylation (adds two OH groups across a double bond, trans to each other)

OsO4 w/ NMO

syn-dihydroxylation (adds two OH groups across a double bond cis to each other)

KMnO4

syn dihydroxylation (adds to OH groups across a double bond, cis too each other)

is a benzylic CH is present, KMnO4 converts alkyl benzenes into benzoic acids (cuts R group/chain off no matter how long and converts to carboxylic acid)