EXAM 4 Orgo I

SN1/2, E1/2, alkene addition

Strong Base, Weak Nucleophile, 1^o

E2

Strong Base, Weak Nucleophile, 2^o

E2

Strong Base, Weak Nucleophile, 3^o

E2

Strong Base, Strong Nucleophile, 1^o

SN2

Strong Base, Strong Nucleophile, 2^o

E2

Strong Base, Strong Nucleophile, 3^o

E2

Weak Base, Strong Nucleophile, 1^o

SN2

Weak Base, Strong Nucleophile, 2^o

SN2

Weak Base, Strong Nucleophile, 3^o

SN1

Weak Base, Weak Nucleophile, 2^o

SN1/E1

*depend on heat (E prefer heat)

DBU

Strong Base, Weak Nucleophile

DBN

Strong Base, Weak Nucleophile

NaH

Strong Base, Weak Nucleophile

t-BuOK

Strong Base, Weak Nucleophile

LDA

Strong Base, Weak Nucleophile

NaOH

Strong Base, Strong Nucleophile

(-)NH2

Strong Base, Strong Nucleophile

(-)OMe

Strong Base, Strong Nucleophile

(-)OEt

Strong Base, Strong Nucleophile

RO-

Strong Base, Strong Nucleophile

I-

Weak Base, Strong Nucleophile

Br-

Weak Base, Strong Nucleophile

Cl-

Weak Base, Strong Nucleophile

-SH

Weak Base, Strong Nucleophile

RSH

Weak Base, Strong Nucleophile

CN-

Weak Base, Strong Nucleophile

RNH2

Weak Base, Strong Nucleophile

R3P

Weak Base, Strong Nucleophile

Et3N

Strong Base, Weak Nucleophile

H2O

Weak Base, Weak Nucleophile

ROH

Weak Base, Weak Nucleophile

RCOOH

Weak Base, Weak Nucleophile

Hydrohalogenation

add H and X

what is the regiochemistry for hydrohalogenation

Markovnikov

what is the stereochemistry for hydrohalogenation

Mix (syn and anti)

what are/is the reagents for hydrohalogenation

HX (Cl, Br, I)

Radical addition of HBr

Add H and Br

what are/is the reagents for radical addition of HBr

HBr, ROOR

what is the regiochemistry for radical addition of HBr

Anti-markovnikov

what is the stereochemistry for radical addition of HBr

Mixed (syn and anti)

what are/is the reagents for acid catalyzed hydration

H3O+, H2SO4 (dil)

what are/is the reagents for oxymercuration-demercuration

1. Hg(OAc)2, H2O

2. NaBH4

what are/is the reagents for hydroboration-oxidation

1. BH3 * THF

2. H2O2, NaOH

what are/is the reagents for catalytic hydrogenation

H2, Pt (Pd, Ni)

what are/is the reagents for bromination or chlorination

Br2 or Cl2

what are/is the reagents for halohydrin formation

Br2, H2O

what are/is the reagents for syn dihydroxylation

KMnO4, NaOH cold; OsO4/NMO

what are/is the reagents for epoxidation

RCO3H (MCPBA)

what are/is the reagents for anti-dihydroxylation

1. RCO3H

2. H3O+

what are/is the reagents for ozonolysis

1. O3

2. DMS or Zn/H2O

Acid catalyzed hydration

add H + OH

oxymercuration-demercuration

add H + OH

hydroboration-oxidation

add H + OH

catalytic hydrogenation

add H + H

bromination or chlorination

add Br + Br or Cl + Cl

halohydrin formation

add Br + OH

Syn dihydroxylation

add OH + OH

epoxidation

for epoxide (with O in the middle)

anti - dihydroxylation

add OH + OH

ozonolysis

cleave C=C; form two C=O group

what is the regiochemistry for acid catalyzed hydration

Markovnikov

what is the regiochemistry for oxymercuration-demercuration

Markovnikov

what is the regiochemistry for hydroboration-oxidation

Anti-markovnikov

what is the regiochemistry for catalytic hydrogenation

N/A

what is the regiochemistry for bromination or chlorination

N/A

what is the regiochemistry for Halohydrin formation

OH to the more substituted

what is the regiochemistry for Syn dihydroxylation

N/A

what is the regiochemistry for epoxidation

N/A

what is the regiochemistry for anti dihydroxylation

N/A

what is the regiochemistry for ozonolysis

N/A

what is the stereochemistry for acid catalyzed hydration

Mixed (syn and anti)

what is the stereochemistry for oxymercuration-demercuration

Mixed (syn and anti)

what is the stereochemistry for hydroboration-oxidation

Syn

what is the stereochemistry for catalytic hydrogenation

Syn

what is the stereochemistry for bromination or chlorination

Anti

what is the stereochemistry for halohydrin formation

Anti

what is the stereochemistry for syn dihydroxylation

Syn

what is the stereochemistry for epoxidation

adds to one face

what is the stereochemistry for anti dihydroxylation

Anti

what is the stereochemistry for ozonolysis

N/A

SN1 in what solvent

HAS to be polar protic

SN2 in what solvent

polar aprotic

E2 in what solvent

polar aprotic is faster but protic is fine

E1 in what solvent

polar protic solvent

SN1 order of faster reaction

3 > 2

SN2 order of faster reaction

methyl > 1 > 2

E1 order of faster reaction

3 > 2

E2 order of faster reaction

3 > 2 > 1

stereoselectivity at SN2

inversion at chiral center

stereoselectivity at SN1

Racemization at chiral center

stereoselectivity at E2

Anti periplanar between LG and beta hydrogen

stereoselectivity at E1

None

Polar protic

Can donate hydrogen bonds.

Stabilize carbocations and anions.

Strongly solvate nucleophiles, especially negatively charged ones, reducing their nucleophilicity.

Polar protic ex.

water, alcohol, carboxylic acid

Polar Aprotic

Cannot donate hydrogen bonds.

Solvate cations well but do not strongly hydrogen-bond to anionic nucleophiles.

Leave anionic nucleophiles relatively reactive.

• easier for the NU to attack

Polar aprotic ex.

DMSO (dimethyl sulfoxide)

DMF (dimethylformamide)

Acetone

Acetonitrile (CH₃CN)