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Chemistry 22: Some Notes On Chapter 10 Reactions: Y Y Y Y

I. The chapter discusses reactions of three-membered rings and addition stereochemistry. Nucleophiles approach based on ring structure and substitution. Addition can be anti or syn. II. Bromination, chlorination, and hydration reactions proceed with net anti addition through bromonium or chloronium intermediates. Oxymercuration-reduction and epoxidation retain alkene stereochemistry. III. Epoxide openings in acid/base give anti addition back to the original alkene. Hydrogenation is syn addition and stereoselective based on steric effects.

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77 views

Chemistry 22: Some Notes On Chapter 10 Reactions: Y Y Y Y

I. The chapter discusses reactions of three-membered rings and addition stereochemistry. Nucleophiles approach based on ring structure and substitution. Addition can be anti or syn. II. Bromination, chlorination, and hydration reactions proceed with net anti addition through bromonium or chloronium intermediates. Oxymercuration-reduction and epoxidation retain alkene stereochemistry. III. Epoxide openings in acid/base give anti addition back to the original alkene. Hydrogenation is syn addition and stereoselective based on steric effects.

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hairey947594
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Chemistry 22: Some Notes on Chapter 10 Reactions

I. Two important themes:


A. Opening of neutral and positively charged three-membered ring structures:
1. Always anti stereochemistry.
2. Neutral three-membered ring structure: nucleophile approaches the less
substiututed carbon.
3. Positively charged three-membered ring structure: nucleophile
approaches the more substiututed carbon.
Y
Nuc
Y
Nuc
Nuc
Y
Y
Nuc

B. Anti and syn stereochemistry of addition:
Y
X
Y
X
anti addition
syn addition


Note that anti and syn here describe the stereochemistry of the addition
process, and not necessarily of the product structures.


X
X
X
X
X X
syn
addition
syn
addition
=
anti addition
X X
=

II. Bromination, chlorination, bromohydrin formation, and chlorohydrin
formation (bromonium and chloronium ion intermediates).
(racemic)
Br
2
CCl
4
CH
3
Br
Br
(racemic)
Br
2
H
2
O
CH
3
OH
Br
(racemic)
Br
2
ROH
CH
3
OR
Br
(racemic)
Cl
2
CCl
4
CH
3
Cl
Cl
(racemic)
Cl
2
H
2
O
CH
3
OH
Cl
(racemic)
Cl
2
ROH
CH
3
OR
Cl

Always net anti addition.

III. Oxymercuration-reduction.
Reaction accomplishes the same thing as addtion of H
3
O
+
(Markovnikov addition of
H
2
O or ROH), but without the risk of carbocation rearrangements).
1) Hg(OAc)
2
/THF/H
2
O
2) NaBH
4
OH
H
3
O
+
H
2
O
OH
OH
But:
and

1) Hg(OAc)
2
/THF
CH
3
CH
2
OH
2) NaBH
4
O
Alkoxymercuration:


IV. Epoxidation.
CF
3
CO
3
H
CF
3
CO
3
H
O (racemic)
O
CF
3
CO
3
H
O
(racemic)

H
O
O
O CF
3

Stereochemistry of alkene is retained.
mCPBA (meta-chloroperoxybenzoic acid) can also be used in place of CF
3
CO
3
H.

V. Opening of epoxides in acid and base.
O
H
2
O
acid or base
OH
OH
(racemic)
O
CH
3
OH
acid
O
CH
3
OH
base
OCH
3
CH
3
OH
H
CH
3
OH
H
OCH
3
(racemic)
(racemic)
Starting from an alkene which is
epoxidized (previous reaction),
the net result is always anti
addition across the double bond.
The epoxidation reaction is
concerted and preserves the
stereochemistry of the alkene.


VI. Hydrogenation.
A. Reaction: addition of H
2
across an alkene.

H
2
Pd/C or Pt/C

B. A stereospecific syn addition.
and
(racemic)
meso
H
2
Pd or Pt
H
2
Pd or Pt
H
2
Pd or Pt

C. Stereoselectivity: steric effects.
H
3
C
CH
3
H
3
C
CH
3
CH
3
H
H
2
Pd or Pt

D. Hydrogenation of alkynes (C!C to C=C or C-C).
1. H
2
& Pd catalyst " alkane.
2. H
2
& Lindlar!s catalyst " cis alkene.
3. Na/NH
3
" trans alkane.

H
2
Pd/C (or Pt)
H
2
Lindlar's Catalyst
Na/NH
3
(or Li/NH
3
)


VII. Carbenes: cyclopropanation.
CH
2
N
2
(racemic)
CHCl
3
KOH
Cl Cl
CH
2
I
2
Zn(Cu)
(racemic)

Stereochemistry of alkene is preserved.

VII. Ozonolysis.
1) O
3
2) [H]
O
O
H
1) O
3
2) [O]
O
O
OH
1) O
3
2) [H]
H
O
O

[H] = Zn/H
2
O OR (CH
3
)
2
S OR H
2
/Pd.
[O] = H
2
O
2
/HOAc.

IX. Hydroxylation: OsO
4
/NaHSO
3
.
(racemic)
1) OsO
4
2) Na
2
SO
3
H
2
O
CH
3
OH
OH
H

The above is a syn addition; contrast to the anti addition below.
(racemic)
1) CF
3
CO
3
H
2) H
2
O/
acid or base
CH
3
OH
H
OH

X. Addition reactions of alkynes are (roughly) analogous to those of alkenes.

R
HX
R
X
R
X X
R
X
2
R
X
R
X X
X
X
X
R
R
OH
R CH
3
H
2
O/H
+
Hg
++
O
R
R
R
1) R'
2
BH
2) H
2
O
2
NaOH
OH
O
H
R R
H
2
Lindlar's
Catalyst
Na/NH
3
R R
R
R
R R
(Markovnikov)
(Markovnikov)
(anti-Markovnikov)
H C C H
NaNH
2
H C C
R X
H R
NaNH
2
R C C
R' X
R R'
R, R' must be 1 (S
N
2) X = good LG (e.g., OTs, I, Br, Cl)
H
H
H
H
=
=
R R
R
R

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