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The Felkin Anh Model, Lecture notes of Organic Chemistry

Felkin-Anh. Anti-Cram or. Cram Chelate. S = Small. M = Medium. L = Large. The Felkin Anh Model. Chem. Rev. 1999, 99, 1199. Page 2. The Cram Chelate Model.

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L
M
S
O
Nu-
Anti-Felkin
L
M
S
O
R
Nu-
Felkin
103°
R
L
M
SR
HO
Nu
L
M
SOH
R
Nu
Felkin-product anti-Felkin-product
L
O
R
M
Snucleophile
LNu
M
S
OHR
LNu
M
S
RHO
Cram or
Felkin-Anh
Anti-Cram or
Cram Chelate
S = Small
M = Medium
L = Large
The Felkin Anh Model
Chem. Rev. 1999, 99, 1199
pf3
pf4
pf5

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L

M

S

O

Nu

Anti-Felkin

L

M

S

O

R

Nu

Felkin

R

L

M

S

R

HO

Nu

L

M

S

OH

R

Nu

Felkin-product anti - Felkin-product

L

O

R

M

S

nucleophile

L

Nu

M

S

R OH

L

Nu

M

S

HO R

Cram or

Felkin-Anh

Anti-Cram or

Cram Chelate

S = Small

M = Medium

L = Large

The Felkin Anh Model

Chem. Rev. 1999 , 99 , 1199

The Cram Chelate Model

L

O

R

M

S

nucleophile

L

Nu

M

S

R OH

L

Nu

M

S

HO R

Cram or

Felkin-Anh

Anti-Cram or

Cram Chelate

S = Small

M = Medium

L = Large

O

R

Met

L

M

S

Nu

L

M

S

R

Nu

OH

anti - Felkin-product

L = OR', NHR',...

The Felkin Anh Model

L

M

L

M

Nu

OH

L

M

Nu

HO

O

R

2 ) H

1 ) M Nu

Entry FA : CC

Felkin-Anh (FA) Cram-Chelat (CC)

M Nu

R

R

S

S

S

M

L

S R

Ph 19 17 : 83

p - Tol

Ph 20 02 : 98

Ph 21 04 : 96

p - Tol

Ph 22 12 : 88

Ph

Ph 23 34 : 66

Ph

NBn

2

Me

13 95 : 05

NBn

2

Me

14 06 : 94

Ph

SMe

Et

15

Li(

s

Bu)

3

BH

Ph

CO

2

Me

Me

17 73 : 27

Ph

Me

18 03 : 97

Ph

SMe

Et

16 06 : 94

Ph

H LiAlH

4

H PhMgBr

H CH PhMgBr

3

CH

3

PhLi

OH

OH

OH

OH

CH

3

MeMgBr OH

CH

3

H H MgBr

CH

3

TiCl

3

H H

CH

3

H NaBH

4

NHAc

H

KBH

4

H

CO

2

Me

Zn(BH

4

2

H

Zn(BH

4

2

H

Felkin-Anh or Cram Chelate?

O O

H

O

O O

Nu

OH

O O

Nu

OH

Felkin-product anti - Felkin-product

nucleophile

L=O...

M=CH

2

O...

nucleophile FA:CC

allylMgBr 60:

allylTi(O

i

Pr) 3

(allyl) 2

Zn 90:

PhLi 48:

PhMgBr 48:

PhTi(O

i

Pr) 3

MeLi 60:

MeMgBr 67:

n

BuLi 69:

n

BuMgBr 75:

i

BuMgBr 75:

n

BuTi(O

i

Pr)

3

Li

Li

Li CH(OEt)

2 70:

S S

Ph Li , Ti(O

i

Pr)

4

S S

Ph Li

, Zr(O

i

Pr) 4

S S

Ph Li

, ZnBr 2

S S

Ph Li

, MgBr 2

B(O

i

Pr)

2