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Substitution Summery

Substitution Summery

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Published by Siddarth Singh

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Published by: Siddarth Singh on Apr 14, 2012
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10/22/2013

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Summary of Chapter 11 MaterialSN2 Reaction
Substrate
:
NO SN2 ON A TERTIARY HALOALKANE!!
order of reactivity is as follows: Methyl > 1 > 2Sterically less hindered substrates have faster rates in SN2
Nucleophile
: If the reacting atom is the same in a series, nucleophilicityparallels basicity (i.e. -OH > -OCH
3
> -OCH
2
CH
3
> H
2
O)For the halogens in
GAS PHASE
: F
-
> Cl
-
> Br 
-
> I
-
For the halogens in
SOLUTION
: I
-
> Br 
-
> Cl
-
> F
-
(due tosolvation of nucleophile, rendering it inactive)Negatively charged nucleophiles give neutral productsNeutral nucleophiles give cationic productsIn
SOLUTION
nucleophilicity increases down a column in theperiodic table (i.e. -OCH
3
> -SCH
3
> -SeCH
3
)Anionic nucleophiles are usually stronger than neutral ones
Leaving Group
: Best leaving groups are those that best accomodate anegative charge (large anions such as I
-
)The best leaving groups are
WEAK BASES
  According to this criteria, the worst leaving groups are: 
F-, OH-, OCH
3
-, CN-, N
3
-, NH
2
The best leaving groups are:
H
2
O, CH
3
OH, OTs, I
-
Notes
: The SN2 reaction is bimolecular - it depends on amountsof nucleophile and leaving groupIn synthesis, always convert an OH leaving group into anOTs leaving groupConverting an OH into an OTs will
NOT
change thestereochemistry!!SN2 reaction goes with inversion about the stereogeniccarbon
Solvent
:
Polar protic
solvents are the worst for SN2; theysolvate the nucleophile so it cannot attack 
Polar aprotic
solvents stabilize the transition state andspeed SN2 reactions upPolar aprotic solvents are DMSO, DMF, CH
3
CN, HMPA
SN1 Reaction
Substrate
: SN1 reactions work best on a
TERTIARY
! 
NO SN1 ON A PRIMARY!!
Order of reactivity: 3 > 2Benzylic and Allylic carbons have increased reactivitybecause of resonance stabilization
Nucleophile
: Has
NO
effect upon the rate of reaction!! Rate limiting stepdoes not include the nucleophile!!To convert OH to a good leaving group use HX
Leaving Group
: Same as for SN2 reactions!!
Solvent
:
Polar aprotic
solvents work well 
Polar protic
solvents work even better because theystabilize the carbocation intermediate
Notes
: SN1 is unimolecular and depends only on amount of substrate!SN1 goes through a carbocation intermediateStereochemistry is lost during an SN1 reaction and theproducts usually display a small excess of inversion productWatch out for 
CARBOCATION REARRANGEMENTS
!

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