Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof.

Robert Batey, Page 1

Understanding Organic Reactions Electron-Pushing or Arrow-Pushing

Pictoral depiction of a reaction mechanism showing changes in bonding. Shows how electrons "move" in the conversion of reactant(s) to product(s), specifically how bonding pairs of electrons (i.e., covalent chemical bonds) and lone-pairs of electrons change. Movement of 2-electrons is depicted by a curved single-headed arrow. These arrows show the making and breaking of bonds.

"tail" of arrow electrons emanate from a "source" i.e., from a non-bonded lone pair of electrons or from a or a -bond

"head" of arrow electrons "flow" in this driection toward an electron "sink" i.e., toward an atom or bond that can accept an electron pair, such as a * or p* molecular orbital or an empty atomic orbital (e.g. d-orbital)

Example: the SN2 Reaction - Anatomy of an "Electron-pushing" Mechanism

electrons "flow" from a nonbonded pair of electrons on the oxygen atom, toward the electrophilic C-atom, making a new CO -bond the species bears a formal -ve charge the double dagger depicts a the dotted line depicts a transition state partial bond

H H
H O H C

H
Cl

H H
C

H
C H H Cl

H H
HO C H H C

C H

SN2

H
Cl

HO

reactants
electrons simultaneously "flow" toward the Cl atom, breaking the CCl -bond

transition state

products
reaction arrow

In many cases we abbreviate the structures and mechanism, by (i) not showing a transition state, (ii) not showing all CH bonds, and (iii) not showing all or any of the lone-pairs of electrons. Thus the mechanism shown above can be redrawn as:
SN2

HO Cl

OH

Cl

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 2

Understanding Organic Reactions Electron-Pushing or Arrow-Pushing

Most organic reactions involve those between a nucleophile and an electrophile, in which just one new sigma-bond is formed. There are two notable exceptions, (i) free-radical reactions, and (ii) pericyclic reactions. We will see a few examples of these reactions later in the course. Nevertheless, the vast majoirty of reactions that you will see involve nucleophile - electrophile reactions.
In many mechansims more than one curved arrow is shown for a step of a reaction. The curved arrow which shows the new sigma-bond being formed can be used to identify which component is the nucleophile and which is the electrophile. Considering the case of a nucleophilic displacement (SN2 reaction) shown again below. Here the oxygen atom of the hydroxide anion is the nucleophilic atom, whereas the C of the CCl bond is the electrophilic atom. We say that the hydroxide is the nucleophile (the electron pair donor) and the chloroethane is the electrophile (the electron-pair acceptor)
electron movement showing a bond being made HO Cl nucleophilic centre electrophilic centre electron movement showing a bond being broken SN2 OH

Cl

Now consider the more complex mechanisms shown below:

electron movement showing a new sigma bond being made
N O OCH3

O OCH3

nucleophilic centre

electrophilic centre
electron movement showing a new sigma bond being made

O C H3C
nucleophilic centre

Br CH2

Br
C H3C C H H Br Br

electrophilic centre

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 3

Understanding Organic Reactions Electron-Pushing or Arrow-Pushing

We should carefully distinguish the various arrow types we use in organic chemistry:
reaction arrow

or

equlibrium arrow

electron-push depicting involvement of 2-electrons

resonance arrow

fishhook arrow: electron-push depicting involvement of 1-electron (note the head of the arrow only has one hook)

retrosynthetic arrow

It is essential that you show the correct arrows when you draw reactions/mechanisms! If you use the wrong arrow, it shows an improper understanding of organic chemistry (you will lose points on an exam).

For example what is wrong with the following scheme? O N

O N

The electron pushcing is correct, as are the two structures! What then is the problem? The arrow interconnecting the two structures is a "reaction arrow", whereas the two structureas are in fact resonance structures. Therefore a "resonance arrow" should be depicted. You may be asking why is this a problem? As shown the reaction arrow depicts a reaction in which the two structures represent physically distinct species. This is not the case here, since the two "structures" show resonance (the atoms have not changed positions), i.e., the true structure is a hybrid of these structures. (Again it is worth emphasizing that resonance is also not an equilibrium.)

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 4

Classes of Electron "Sources":

1. Non-bonded lone-pairs of electrons on heteroatoms and carbanions, e.g.
R H2O R3N RO RS R e.g. HS O SN2 HS C O N C R C C

Note: it is common to omit drawing lone-pairs that are not directly involved in a reaction. However, you must always draw lone-pairs that are used as "sources" for your electron-flow mechanisms. For example, in the mechanism shown above, only one lone-pair is shown on sulfur in the reactant, whereas in fact there are three lone-pairs on sulfur in HS. Also, there are no lone pairs drawn on the oxygen of the second reactant, or on either of the sulfur or oxygen atoms of the product (in fact there are 2, 2 and 3 lone pairs on these atoms, respectively).

2. Electron-pair from -bonds, e.g. paritcularly electron-rich -bonds, e.g.

C C O R2N

alkenes

aromatics

alkynes

dienes

e.g.

H H

Br

H H Br Note: it is common to omit drawing eithercarbon atoms or the H-atoms on a CH bond. However, it is often useful to draw in the H atoms that are involved or are close to the reacting centres.

3. Electron-pair from electon-rich or strained -bonds, e.g.

H R

Li

MgCl

Al H

cyclopropanes

O e.g. H Li CH3 H H H H3C O Li

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 5

Classes of Electron "Sinks":

1. Acidic hydrogen atoms, usually XH (X=heteroatom) but sometimes CH bonds, e.g.
H H O H e.g. O O H R O H R N H H R O S O O H O H C C H

O R

H H H O

H H

O R

H H H + O

H H

2. Species with unfilled orbitals (i.e., Lewis acids) - usually p- or d-orbitals, e.g.
F M F B F BF3 O C H H H O C H C Si Cl O R RO P Cl

e.g.

BF3

3. Carbon atoms in -bonds, usually polarized such as C=O or C=N (less commonly C=C), e.g.
O C R R R O C Cl R NH C H C C C O

e.g. HO

O C R OCH3

HO C R

O OCH3

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 6

Classes of Electron "Sinks":

4. Carbon atoms in polarized -bonds CX (X=heteroatom), e.g.
R C H H Cl H R C H OSO2R' H R C H O H H

e.g. H H H N H H C H Cl H H H N C H H H Cl

5. Heteroatoms in polarized -bonds XY (X and Y=heteroatoms), e.g.

R Br Br I I R O O R S S R

Note: such -bonds between two heteroatoms are usually quite weak.

H e.g. Br Br Br H Br

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 7

10 Basic Rules of Electron-Pushing:

1. Octet Rule: for first row elements (i.e., C, N, O, F) make sure the octet rule is obeyed. Not obeying the octet rule is a common error. Elements in lower rows of the periodic table also often obey the octet rule, but there are many examples that do not. For example, there are many examples of molecules where P and S obey the octet rule, but others do not, e.g., O=PCl3 can be considered to have 10 electrons around the phosporus atom. This is often rationalized by invoking the use of d-orbitals to accept the additional electrons. 2. Conservation of Charge: the overall combined charge of the reactants should be the same as that for the products. It is a common error to see mechanisms in which the total charge changes. 3. Fomal Charges : ensure that you write correct formal charges for atoms. Also, a common error. 4. Lone Pairs: Similarly draw all relevant non-bonded lone-pairs of electrons. 5. Conservation of Atoms (Matter): ensure that you do not add or lose atoms into your products that were not present in the reactants. This is a remarkably common error, particularly adding or losing H-atoms present as CH bonds, or adding and removing carbon atoms. 6. Direction of Electron "Flow": electrons "flow" from electron-rich sites to electron-poor sites. Not the other way around! Indicating electrons flowing in the wrong "direction" is a very common error, therefore, be careful to avoid pushing electrons in the wrong direction. 7. Positioning of Electron-Flow Arrows: it is important to show the electron-flow arrows at the corrrect positions relative to the bonds in the reactants. This is a common error. 8. Positioning of Atoms: ensure that the connectivity of the atoms in reactants and products is correctly drawn. It is common to see atoms or groups being drawn at the wrong positions in molecules. 9. Show all of the Electon-Flow Arrows: it is common to see mechanisms drawn that have missed out one or more of the electon-flow arrows. 10. Do not combine electon-flow arrows for multiple steps as if they were occuring as a single step: it can be tempting to draw a reactions mechanism as occurring as a single step, even though the reaction takes place via two or more discrete steps. In some cases such mechanisms do not make "chemical sense", whereas in others, although such a mechanism may appear reasonable, experimental evidence may indicate multiple steps. This is another very common error. Finally, one additional "rule" .... 11. Stongly Acidic / Basic Conditions: another very common "mistake" is to show a mechanism that shows both strong acids and bases as coexisting under the same reaction conditions. This is not strictly an electronpushing error, but it is useful to include here, since it is a very common error. Often incorrectly drawn mechanisms/reactants/products combine multiple errors.

In the following examples, comparisons of incorrectly and correctly drawn mechanisms are depicted. Identify the problems with the incorrect mechanisms.

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 8

Mechanisms: Examples of Incorrectly Drawn Products

O N H + H2O incorrect

O O N H O H H N H + H2O incorrect

O N H + H2O correct

O N C
O N C CH3

incorrect

N C O

correct

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 9

Mechanisms: Examples of Incorrectly Drawn Electron-Flow Arrows

O H H H Li O H H H Li+ incorrect

O H H Li H

O H H H

Li+ incorrect

O H H

O H H H Li

Li+
correct

F H HO H F OH
incorrect

F H OH F H OH correct

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 10

Mechanisms: Examples of Incorrectly Drawn Electron-Flow Arrows

N H O H3C H H N incorrect H H3C O H H

N H O H3C H H

N H O H3C H H

HO

Br

H Br H2O incorrect

HO

Br

H Br H2O correct

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 11

Mechanisms: Examples of Violations of the Octet Rule

H3C O H H O

CH3
CH3

O H O H

CH3 incorrect H

O H O H3C

CH3 O H H O H H3C

CH3
correct H H

Li

O H H

O Li

H H incorrect

H Li H O H correct H O Li

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 12

Questions: Identify the Mistakes of the Following Reaction Mechanisms

H (a) H Br H Br H

O (b) H3C C H

Li O C H3C

Li

H (c) H N

O O

H N H

O O

(d) Cl HO H

H2O

Cl

CH3

HO
(e) H3C

CH3 C CH3

HO CH3 CH3

(f) P O

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 13

Questions: Predict the Products of the Following Reactions

(a) N C O

O O O

(b)

O H
(c)

O H3C H
(d)

Cl H

N R R R

R Se O H

(e)

Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 14

Questions: Show the Electron Flow Arrows in the Following Reactions

(a) N C Br N C

O (b)

O H H

O N O

H+ O N O

(c)

R R P R CH2 H

O H

R R P R C H2

O H H

R P R R

O H H H H R R

R P

O C H2 H H