92 views

Uploaded by prejudiced

Powerpoint about pericyclic reactions in organic chemistry including theories.

- Pericyclic Reactions and Organic Photochemistry
- Pericyclic Reactions
- Retrosynthesis Solutions
- Nucleophilic Substitution Reaction (SN2)-1
- Rearrangement Reactions
- Introductory Organic Reaction Mechanisms: A color-coded approach to arrow pushing
- Pericyclic Reactions
- pericyclic reactions
- Pericyclic Reactions
- Organic Synthesis - The Disconnection Approach
- Pericyclic Reaction
- pericyclic reactions.pdf
- Practice Problems-Pericyclic Reactions
- Retrosynthesis Concept
- Multiple Choice Quiz-pericyclic Chemistry
- lecture-7-1
- Problem 1 028
- 23720836-Ultimate-Organic-Chemistry-Mindmap-9746
- Data Sinyal Vibrasi Blower
- heat exchangers

You are on page 1of 29

I. Definitions

A. Cycloaddition

B. Electrocyclic reaction

C. Sigmatropic reaction

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

B. Frontier orbital approach

C. Generalized Woodward-Hoffmann selection rules

III. Transition State Aromaticity

A. Hckel and Mbius aromaticity

B. Interaction diagrams

C. Aromatic and antiaromatic transition states

IV. Summary

2

A

hv

hv

A

Ph

Ph

+

Ph

Ph

CO

2

CH

3

CO

2

CH

3

+

CO

2

CH

3

CO

2

CH

3

hv

A

OAc

H

H

D

A

OAc H

H

D

thermally forbidden

photochemically allowed

photochemically forbidden

thermally allowed

inversion of configuration

3

I. Definitions

A. Cycloaddition

Pericyclic reaction: one in which concerted bond breaking and bond

formation occur through a reorganization of electrons within a closed loop

of interacting orbitals.

Ring formation by transfer of electrons from t bonds to new o bonds.

Cycloreversion: reverse process.

+

t2 + t2

o2 + o2

t4 + t2

o2 + o2

+

t4 + t4

+

t2 + t2

t2 + o2 + o2

t2 + t2

+ o2 + o2

2 + 2 cycloaddition/cycloreversion

4+2

4+4

2+2

4

I. Definitions

A. Cycloaddition

or or

suprafacial (s)

process

antarafacial (a)

process

t4s + t2s

(t2s + t2s + t2s)

(t2a + t2a + t2s)

t4a + t2s

(t2s + t2a + t2s)

(t2a + t2s + t2s)

5

I. Definitions

B. Electrocyclic reaction

Formation of a single bond between the termini of a linear t system,

and the reverse process.

electrocyclic ring closure

electrocyclic ring opening

conrotatory process

disrotatory process

6

I. Definitions

B. Electrocyclic reaction

disrotatory

conrotatory

t6s

(t2s + t2s + t2s)

t4s + o2s

(t2s + t2s + o2s)

t6a

(t2s + t2s + t2a)

t4s + o2a

(t2s + t2s + o2a)

t4a + o2s

(t2s + t2a + o2s)

7

I. Definitions

C. Sigmatropic reaction

Bond migration over a t system.

R R

1

2

3

1'

1'

3

2

1

1

2

3

1'

2'

3'

3

3'

[1,3] sigmatropic shift

[3,3] sigmatropic shift

(Cope rearrangement)

[1,3]

retention

a

c

b

a

c

b

t2s + o2s

supra migration

8

I. Definitions

C. Sigmatropic reaction

a

c

b

a

c

b

[1,5]

inversion

[1,5]

retention

a

c

b

a

c

b

[3,3]

t4s + o2a

(t2s + t2s + o2a)

supra migration

t4a + o2s

(t2a + t2s + o2s)

antara migration

t2s + t2s + o2s

supra/supra migration

9

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

1. cycloaddition/cycloreversion

Woodward-Hoffmann Rules

In any concerted process, the starting material orbitals must be

transformed into product orbitals of the same symmetry.

(There are other symmetry elements as well, but no additional information

is gained; o

1

and o

2

are sufficient to differentiate orbital symmetries.)

o

1

o

2

o

1

o

2

+

10

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

1. cycloaddition/cycloreversion

o

1

o

2

mix t

orbitals

+

o

1

o

2

o

1

o

2

o

1

o

2

mix o

orbitals

o

2

o

1

o

1

o

2

+

not symmetry correct

with respect to o

1

not symmetry correct

with respect to o

2

t

1

- t

2

= t

SS

o

1

o

2

t

1

+ t

2

= t

AS

o

1

+ o

2

= o

SS

o

1

- o

2

= o

SA

11

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

1. cycloaddition/cycloreversion

Orbital correlation diagram:

t*

AA

t*

SA

t

AS

t

SS

o*

AA

o*

AS

o

SA

o

SS

thermally (black):

g.s. upper e.s.

symmetry forbidden

photochemically (blue):

1

st

e.s. 1

st

e.s.

symmetry allowed

12

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

1. cycloaddition/cycloreversion

+

o

o plane is only symmetry element

t orbitals are correct, need to mix os

13

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

1. cycloaddition/cycloreversion

4

A

t

2

A

3

S

2

A

t

1

S

1

S

o

4

A

o

3

S

t

2

A

t

1

S

o

2

A

o

1

S

thermally

allowed,

photochemically

forbidden

avoided crossings

-orbitals of the same symmetry do not cross

14

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

1. cycloaddition/cycloreversion

General for all-supra cycloadditions/cycloreversions:

allowed forbidden

A 4n+2 4n

hv 4n 4n+2

15

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

2. electrocyclic reactions

conrotatory

disrotatory

c

2

axis

o plane

16

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

2. electrocyclic reactions

S

A

S

A

A

S

A

S

A

S

A

S

A

A

S

S

conrotatory (c

2

)

A allowed

hv forbidden

disrotatory (o)

A forbidden

hv allowed

17

II. Conservation of Orbital Symmetry

A. Symmetry correlation diagrams

2. electrocyclic reactions

General for electrocyclic reactions:

A allowed hv allowed

conrotatory 4n 4n+2

disrotatory 4n+2 4n

4n conrotatory disrotatory

4n+2 disrotatory conrotatory

18

II. Conservation of Orbital Symmetry

B. Frontier orbital approach: sigmatropic reactions

[1,3]-H:

suprafacial

antarafacial

No symmetry elements; symmetry correlation diagrams not relevant.

Look at orbital symmetry conservation in HOMO/LUMO:

19

II. Conservation of Orbital Symmetry

B. Frontier orbital approach: sigmatropic reactions

mix

LUMO

HOMO

isolated

orbitals

A forbidden

hv allowed

20

II. Conservation of Orbital Symmetry

B. Frontier orbital approach: sigmatropic reactions

General for sigmatropic reactions:

A allowed hv allowed

[1,3]-H (4n) antara supra

[1,5]-H (4n+2) supra antara

[i,j]-alkyl:

4n supra inversion retention

antara retention inversion

4n+2 supra retention inversion

antara inversion retention

21

II. Conservation of Orbital Symmetry

C. Generalized Woodward-Hoffmann pericyclic selection rules

A pericyclic reaction is thermally allowed if the total number of

(4n+2) s and (4n) a components is odd.

or - If broken down into two electron components, a pericyclic reaction

is thermally allowed if the number of 2s components is odd.

+

+

H H

H

2s + 2s hv allowed

2s + 2s + 2s A allowed

2s + 2s hv

2s + 2a A

2s + 2s hv

2s + 2a A

22

III. Transition State Aromaticity

A. Hckel and Mbius aromaticity

Dewar-Zimmerman Selection Rules

Hckel:

Mbius:

4n+2 e

= aromatic

4n e

= antiaromatic

4n e

= aromatic

4n+2 e

= antiaromatic

phase

inversion

23

III. Transition State Aromaticity

B. Interaction diagrams

Fundamental topology of interacting orbitals:

omit skeletal framework

disregard spatial orientations of orbitals

use p orbitals to represent all orbitals

assign algebraic signs to the orbitals to minimize the number of

phase inversions

= =

= =

24

III. Transition State Aromaticity

B. Interaction diagrams

=

=

Even number of phase

inversions can always

be reduced to zero.

Odd number of phase

inversions can always

be reduced to one.

No phase inversions = Hckel interaction

One phase inversion = Mbius interaction

25

III. Transition State Aromaticity

C. Aromatic and antiaromatic transition states

Examine topology of interacting orbitals in TS:

Hckel Mbius

4n antiaromatic aromatic

4n+2 aromatic antiaromatic

Aromatic TS A allowed (hv forbidden)

Antiaromatic TS A forbidden (hv allowed)

26

III. Transition State Aromaticity

C. Aromatic and antiaromatic transition states

no phase inversions

6 e

Hckel TS

aromatic

A allowed

= =

no phase inversions

4 e

Hckel TS

antiaromatic

A forbidden

27

III. Transition State Aromaticity

C. Aromatic and antiaromatic transition states

=

=

disrot:

conrot:

4 e

Hckel

A forbidden

4 e

Mbius

A allowed

R R

=

4 e

Mbius

A allowed

28

IV. Summary

O

O

+

10 e

supra/supra cycloaddition

2s + 2s + 2s + 2s + 2s

10 e

Hckel TS

A allowed

CH

3

H

H

H

3

C

H

H

=

4 e

supra/antara cycloreversion

2s + 2a

4 e

Mbius TS

A allowed

29

IV. Summary

=

6 e

antara/antara cycloaddition

2s + 2a + 2a

6 e

Hckel TS

A allowed

Ph

Ph

O

O O

O

O

O

Ph

Ph

A

Ph

Ph

4 e

conrotatory

electrocyclic ring opening

2s + 2a

4 e

Mbius TS

6 e

supra/supra cycloaddition

2s + 2s + 2s

6 e

Hckel TS

- Pericyclic Reactions and Organic PhotochemistryUploaded bybkwrm18
- Pericyclic ReactionsUploaded byPeter Karuso
- Retrosynthesis SolutionsUploaded byScott Hendricks
- Nucleophilic Substitution Reaction (SN2)-1Uploaded byRamesh Katkam
- Rearrangement ReactionsUploaded bysantiisant
- Introductory Organic Reaction Mechanisms: A color-coded approach to arrow pushingUploaded byMichael S. Leonard
- Pericyclic ReactionsUploaded bytosusmitha2014
- pericyclic reactionsUploaded byNitesh kashap
- Pericyclic ReactionsUploaded byDharva
- Organic Synthesis - The Disconnection ApproachUploaded byMichael Turbyfill
- Pericyclic ReactionUploaded byUrugonda Venumadhav
- pericyclic reactions.pdfUploaded bynofacejack
- Practice Problems-Pericyclic ReactionsUploaded byJethro Sanz
- Retrosynthesis ConceptUploaded byveromendo
- Multiple Choice Quiz-pericyclic ChemistryUploaded byChandrashekhar Singh
- lecture-7-1Uploaded byAngel Rondilla
- Problem 1 028Uploaded byOscar Sanchez
- 23720836-Ultimate-Organic-Chemistry-Mindmap-9746Uploaded byKasih Liyana
- Data Sinyal Vibrasi BlowerUploaded byraesyafu
- heat exchangersUploaded byDionie Wilson Diestro
- Highly Stereoselective Tandem Pummerer ReactionUploaded byKike Meneses
- Extra Classes Year 5(1)Uploaded byCikgu Syarifah
- Main Turbine RecommissioningUploaded byabhishekact
- 034-042Uploaded bysmhea123
- Chapter Questions AnswerUploaded byVinny.D
- enone photochemistryUploaded bySwati Gautam
- Ether SynthesisUploaded byaabbcc1311
- RE13 16Uploaded byEko Prastyo
- Practice Chapter 19 QuesUploaded byRosalina Caba

- Mong Project OutlineUploaded byAmir Amirrzz
- (8) Why Do People Find Mathematics Difficult_ - QuoraUploaded bykale sanjay
- Sinamics v20 Pid Functionality v1Uploaded byDjkaoz Erick
- dc score requirement chart 2017-18Uploaded byapi-305517815
- SphereUploaded byhammoudeh13
- Computational Modeling of Genetic and Biochemical NetworksUploaded byMarcus Braga
- Math 116 week 4 answersUploaded byhomeworkanytimehelp
- q. bankUploaded byvrihad
- implicit-interaction.pdfUploaded bySayonara
- Power Oscillation Damping Using FACTS Device Modal Controllability, Observability in Local Signals, And Location of Transfer Function ZerosUploaded byMd. Arifur Kabir
- SeisCapUploaded byamitd010
- ReliabilitySoftwareUploaded byFerOlivares
- PCP HandoutsUploaded byMichael Belostoky
- Fast Deviation Simulation for ‘Fused Deposition Modeling’ ProcessUploaded byChris Burger
- GE263 Lecture NotesUploaded byFares
- 1081ch2_14.pdfUploaded byCristopher Entena
- Network Hubs in the Human BrainUploaded bymir_jeong_1
- QC toolsUploaded byIzzuddin Khairuddin
- Some Important programs on Strings(in C)Uploaded byAnik
- 33363-32962-2-PBUploaded byskrtamil
- uniform circular motion labUploaded byapi-346003119
- Forex Report - Predicting Price MovementUploaded bymohora
- Test Item AnalysisUploaded byDione Christy Yap Brua
- Monopolistic Market @ Bec DomsUploaded byBabasab Patil (Karrisatte)
- IJIRAE:: Finite Element Analysis of Stacker Mechanism used in Bearing ManufacturingUploaded byIJIRAE- International Journal of Innovative Research in Advanced Engineering
- Math SyllabiUploaded byPeter Gates
- STEC_RefGuide_V3.0Uploaded byJaime Fernández Wohlenberg
- Febmarch 2012 NSC Mathematics P1 Feb-March 2012 Memo Eng.pdfUploaded byBalkis
- Instructional ObjectivesUploaded byFem FEm
- Exercise Sheet 3Uploaded byaisyah