Reaction Mechanism

(CHEM-563)

Online Lecture-7 (Week-3)

Dr Abdul Rauf Raza

(Associate Professor)
Department of Chemistry
University of Sargodha, Sargodha
 Addition Reactions
Upper Surface

O
E Products Nu
R
Bottom Surface H
O
X
Re face Si face Nu Products E R
R H R Enol form
X = O, S, NR

O
R
R
Keto form
H
 Mode of Additions
R
R RR Syn Addition
A
(Angle = 0o)
BA
B H
H H
H
Anti Addition
R
R (Angle = 180o)
RR RH
A B
A A
B B
B H R
H H H
H
 R
Syn Additions
Mirror
R RR R R
H
D H H D
=
H HH D H H D
D
cis D D R R
D Erythro
Ni, Pd, Pt, Rh metal
R
H RH RH
O O
Os VIII [O]
O OH =
O O O VI OH
R Os R
R H O H
H Osmate O Mirror
trans O O R R
HO H H OH
H OH H OH
H OH HO H
H OH HO H
R R
OH OH Threo
Erythro Threo
 Syn Additions (Oxidation of Osmate)
O
RH RH RH
N
O O O
O O O O O
R Os R Os R VIIIOs
O H H
H O N O H O
1 O 3 O 4 O O
2
H2O
RH RH RH
H2O
OH O O
OH OH O O O
R R Os R
H H H Os
7 O H
HO
O O O O H
6 5
 Anti Addition
R
R RR R
X R
X
X X X
X X
H H
H H 2 H 3
1 H cis X = Cl, Br, I
R
H X
R R R X H
X H Threo R
= X X
Threo H X 4
R H H
 Anti Addition
OH
Cl
R O
H H RR R
O H
O Cl H2O O HO OH
O
H R
R H 2 (Epoxide) H 3
1 H trans m-CPBA
R
H OH
R R R H OH
HO H R
Erythro = HO OH
HO H 4 Erythro
R H H
 Syn vs Anti Addition
S OH R OH

S OH R OH

m-CPBA

S Br R Br R OH S OH
Br2 i) OsO4
ii) NMPO
S Br R Br S OH R OH

HOBr

S Br R OH

S OH R Br
 Ozonolysis (Syn Addition)
O O
O O O O
O O
O 3 O2 2 O3
1o-Ozonide

O O OH OH
Zn / MeCOOH O O NaBH4
+ +
O
2o-Ozonide
H2O2
O O NH3 / H2 NH2 NH2
+ +
OH
Hydroboration (Syn Addition)

H BHR2 H BR2
H B
R
R Transition State

R R
R2BH B + B
R R
1 2 3
 Preparation of OrganoB
B2H6 H H
B H H
Disiamylborane (Sia2BH) B B
B2H6 H H H
BH2
B2H6
Thexylborane (ThBH2)
B2H6 H
BH B
HB

1,5-COD
9-Borabicyclo[3.3.1]nonane (9-BBN)
 Molecular Orbital Approach (C=C)
E Products

 C C

Insignificant MO C C

 C C

Significant MO
 Molecular Orbital Approach (C=O)
X
Re face Si face Nu Products
R H
X = O, S, NR

Nu
Nu + +
Significant Interation C O Insignificant Interaction
(Steric factor)
(Angle = 107o)
+ +

Nu
Nu
 Nucleophiles
Such soft basess (electron pair donors), which carries a -ve charge
or a non-bonding electron pair on a low electronegative atom
with low charge density are called Nucleophiles.
Hard Nucleophiles
(F-, -OH, OR, H2O, ROH, B C N O F
-
Cl, NH3, RMgBr, RLi)
Nucleophiles

EN
Soft Nucleophiles Cl
(I-, RS-, RSe-, S2-, RSH, CD
R3P, Aromatic rings)
Br
Boarderline Cases
(-N3, -CN, RNH2, R2NH,
R3N, Br-)
I
 Enolization
H
O O B O O

Ar Ar Ar Ar
H
Keto-form Enol-form Enolate
O O O
O
Ar Ar Ar
Ar
(E)-Enolate Enolate (Z)-Enolate

O O O OH O O

Ar R Ar R Ar R

Less stable More stable

 Aldol Reaction
O O OH
O O OH
+ +
R R
R R
O
Cross-Aldol Condensation
R
O OH OH O O
Base
+ +

O
Self-Aldol Condensation

O O O OH O OH
+ +
Et Et Et
 Suggested Reading

i) Chapter 19 (Page 446 to 447)

ii) Chapter 20 (Page 449 to 459)
of “Organic Chemistry” by Clayden, J;
Greeves, N; Warren, S., 2nd Edition, Oxford
University Press, England (2008)