Arrow Pushing and Alkene Addition Reactions

Drawing Electron Pushing Arrows In Alkene Addition Reactions

The last two posts have been about a pretty amazing new concept. Not only can lone pairs act as nucleophiles…. but π bonds can too! In this post we try to rationalize how to draw out the curved arrows that depict the mechanism for these reactions – in other words, the “directions” for telling us which bonds form and which bonds break.

This post is about trying to understand the curved arrows.  It might be a bit esoteric… but esoteric is what we do here at MOC.

Table of Contents

1. Alkenes Can Be Nucleophiles!  But How Do We Draw The Curved Arrows?
2. The Conventional Approach For Drawing Curved Arrows In Alkene Addition Reactions Is Slightly Ambiguous
3. Modified Curved Arrow Convention #1: “Bouncy” Arrows.
4. Modified Curved Arrow Convention #2: “Pre-bonds”. 

1. Alkenes Can Be Nucleophiles!  But How Do We Draw The Curved Electron-Pushing Arrows?

Alkenes are a lot more exciting than they’re often given credit for.  That means that given a sufficiently frisky electrophile, they can donate their pair of π electrons to form a new sigma bond.

Like this!

However, there’s one little problem here. See that curved arrow? What does it really mean? If you weren’t given the product, would you be able to draw it, given that curved arrow?

See the problem here: Which atom of the alkene is actually forming the bond to hydrogen?  When we were dealing with lone pairs, it was easy: atoms clearly “own” their lone pairs, and we can tell exactly which atom is forming a bond to which. With alkenes, it’s different: since they “share” that pair of electrons, we’re going to have to somehow show which atom gets the new atom and which is left behind as a carbocation.

2. The Conventional Approach For Drawing Electron-Pushing Curved Arrows In Alkene Addition Reactions Is Slightly Ambiguous

Here’s the conventional way it’s done. If we want to show the bottom carbon forming the bond, the usual way to do this is to draw this loop like this, to show the “path” of the electrons coming in an arc from this direction. The carbon on the alkene “closest” to the hydrogen is the one that ends up bonded to it.

Similarly, if we wanted to show the left carbon forming the bond, we’d “arc” the bond like this:

One problem with this: it’s kind of a kludge. The curved arrow notation is limited in that all we can really do is decide where the tail should go (at the π bond, obviously) and where the head should go (to form the new bond). But the question of which carbon forms the bond is still ambiguous. 

And if there’s one thing organic chemists hate, it’s ambiguity.

Give me clear definitions or give me death!

To try and deal with this issue, organic chemists have come up with two potential solutions. They’re worth looking at if you’re finding this issue confusing.

3. Modified Electron-Pushing Arrow Convention #1: “Bouncy” Arrows. 

Instead of showing the curved arrow as a big sweeping arc, one solution is to put an extra bounce into the arrow. The idea here is that we’re showing the pair of electrons travelling to the carbon in question, and from there moving on to form the  new sigma bond. No more ambiguity here. [Note 1]

This solves the ambiguity problem at the expense of putting in an extra hump in the arrow. Although it doesn’t seem like a big deal, the extra bounce has likely been the reason why this convention hasn’t taken off.

However well intentioned, the trouble with a convention like this is humanity’s natural tendency towards laziness: taking the time to consistently draw an extra hump into the arrow – even if it takes only 5 seconds – represents extra work that is skipped unless absolutely necessary. Behavioral change is very difficult.

4. Modified Curved Arrow Convention #2: “Pre-bonds”. 

If you find yourself confused following the movement of electrons in the reactions of alkenes with electrophiles, these supplementary conventions might be of use to you.

Personally, even though conventional curved arrows suffer from a bit of ambiguity, that’s generally not enough to make me stop using them. YMMV.

In the next post we’ll resume our regularly scheduled program on alkenes and carbocations.

NEXT POST: Addition Pattern #1 – The Carbocation Pathway 

Notes

Note 1. See this reference for example:

New Bouncing Curved Arrow Technique for the Depiction of Organic Mechanisms
Andrei R. Straumanis and Suzanne M. Ruder
Journal of Chemical Education 2009 86 (12), 1389
DOI: 10.1021/ed086p1389