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Reactions of Alkenes:

Stereochemistry of addition 1) anti-addition


Br2 Br + Br (R,R) (S,S) Br Br

Organic Chemistry Chem-233 George O'Doherty

enantiomers

R1

R2

Br2 R1

Br R2 + R1

Br R2 Br (S,S) Br R2 + R1 Br (S,R) R2 enantiomers but when R1 equals R2 then meso, hence they are the same enantiomers

Br (R,R) Br R1 Br (R,S)

R1

R2

Br2

2) anti-addition
mCPBA meso H3O+ OH + OH (R,R) H3O+ R1 OH R2 + R1 (S,S) OH R2 OH (S,S) enantiomers OH OH enantiomers

R1

R2

mCPBA

R1 O

R2 +

R1 O

R2

enantiomers but when R1 equals R2 then meso

OH (R,R)

R1

R2

mCPBA R1

R2

O R1

R2

H3O+ R1

OH R2 + R1

OH R2 enantiomers but when R1 equals R2 then meso

enantiomers

OH (R,S)

OH (S,R)

3) anti/anti = Net syn-addition


Br R1 R1 R2 Br2/H2O R2 + R1 Br (R,R) Br R2 + R1 R2 OH R2 R1 strong base O (S,R) R2 + O (R,S) R1 R2

OH (R,R) OH R1 Br (S,S) OH R1 Br R2 + R1

OH (S,S) Br R2

enantiomers but when R1 equals R2 then meso

R1

R2

Br2/H2O

(R,S) Br R1 R2 OH (S,R) +

R1

OH (R,S) OH R2

strong base

O R1

R2

O + R1 (S,S) enantiomers

R2

(R,R)

Br (R,S)

Reactions of Alkenes
Radical Bromination
Br Br2 h, AIBN, or peroxides Br NBS h, AIBN, or peroxides

Organic Chemistry Chem-233 George O'Doherty


Chemoselectivity: allylic and benzylic C-H bonds are preferred
Br Br2 h, AIBN, or peroxides Br NBS h, AIBN, or peroxides

Dehydrohalogenation
Br Strong Base MOR M = Li, Na, K R = Me, Et, etc

Stereochemical Aspects of the reaction: Anti-elimination is preferred


Br D D Strong Base D

t-Bu is best
MNR2 M = Li, Na, K R = Me, Et, etc

i-Pr is most comon

Addition of HX across an alkene


X HX X = Cl, Br, I

Stereochemical Aspects of the reaction: addition is stereo-random


X DX D

Regiochemical Aspects of the reaction: Markovnikov addition


CH3 X HX CH3

Addition of HX across an alkene under radical additions


X HX DX X = Cl, Br, I h, AIBN, or peroxides peroxides D

Stereochemical Aspects of the reaction: addition is stereo-random


OMe

Regiochemical Aspects of the reaction: anti-Markovnikov addition


CH3 HX peroxides X CH3

Reactions of Alkenes:

continued

Organic Chemistry Chem-233 George O'Doherty

Addition of HX across an alkene in a participating solvent


Stereochemical Aspects of the reaction: addition is stereo-random
CH3 DX MeOD MeO D CH3

OR 1% Strong acid ROH Acid = HCl, H2SO4, H3PO3, RSO3H R = H, Me, Et, etc

Regioochemical Aspects of the reaction: Markovnikov addition

Addition of X2 across an alkene


X X2 X = Cl, Br, sometimes I X

Stereochemical Aspects of the reaction: anti-addition


X X2 X

Addition of X2 across an alkene in a participating solvent


OR X2 ROH X = Cl, Br, sometimes I R = H, Me, Et, etc X CH3 X2 MeOH X

Stereochemical Aspects of the reaction: anti-addition


MeO CH 3

Regioochemical Aspects of the reaction: Markovnikov addition

Addition of Hg(OAc)2 across an alkene in a participating solvent


OR Hg(OAc)2 ROH R = H, Me, Et, etc NaBH4/O2 OR OH HgOAc NaCl OR HgX NaBH4 OR H

Stereochemical Aspects of the reaction: First step is an anti-addition


CH3 Hg(OAc)2 ROH R = H, Me, Et, etc H3C OR HgOAc

Stereochemical Aspects of the reaction: Second step is stereo-random


OR HgX NaBH4 OR H

Regioochemical Aspects of the reaction: Markovnikov addition

NaBH4/O2

OR OH

Reactions of Alkenes:
Oxidations

continued (part III)

Organic Chemistry Chem-233 George O'Doherty

Epoxidation of alkene
1) Peracids O RCO3H mCPBA Cl CO3H

example (mCPBA)

1) via Bromohydrins Br2/H2O

Br OH Srong base KH NaH LiH or KOt-Bu or KNR2

also NBS or Cl2 or I2

Dihydroxylation of alkene
1) Osmium Tetroxide (OsO4) OsO4 O O O Os O OH H2O OH + OsO3 OsO3 H2O2 OsO4

2) catalytic Osmium Tetroxide (OsO4) with co-Oxident O O O Os O OH H2O OH + OsO3 co-[O] = H2O2, R3NO, I2, or Fe(III)

1% OsO4 co-[O]

co-[O]

3) diols from Oxamercuration/oxidation OH Hg(OAc)2 H2O HgOAc NaBH4/O2 OH OH + OH OH

OH NaBH4

Reactions of Alkenes:
Oxidations

continued (part IV)

Organic Chemistry Chem-233 George O'Doherty

Epoxidation of alkenes
O RCO3H 1) Br2/H2O 2) Srong base O (R,S) achiral becasue meso

R1

R2

RCO3H

H R1

H R2

(R,S) and (S,R) achiral when R1=R2

O R2 R1 R2 1) Br2/H2O 2) Srong base R1 (+/) O

(R,R) and (S,S)

(+/) O R2 R1 (+/) 1) Br2/H2O 2) Srong base H R1

R1

R2

RCO3H

(R,R) and (S,S)

R1

R2

H R2

(R,S) and (S,R) achiral when R1=R2

(+/)

Epoxidation/hydrolysis of alkenes
1) RCO3H 2) H3O+ OH OH (R,R) and (S,S) (+/) 1) RCO3H 2) H3O+ HO R1 (+/) 1) RCO3H 2) H3O+ R1 OH R2 (R,S) and (S,R) achiral when R1=R2 OH R2 R1 OH R2 OH (+/) (R,R) and (S,S)

R1

R2

R1

R2

OH (+/)

Dihydroxylation of alkenes
OH OsO4 OH (R,R) and (S,S) (+/) OsO4 HO R1 (+/) OH R1 R2 OsO4 R1 R2 (R,R) and (S,S) OH R2 R1 OH R2 OH (+/) (R,S) and (S,R) achiral when R1=R2

R1

R2

OH (+/)

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