Organic Reagents

By James Ashenhurst

Reagent Friday: BH3 (Borane)

Last updated: January 29th, 2020 |

BH3 (Borane) 

In a blatant plug for the Reagent Guide, each Friday  I profile a different reagent that is commonly encountered in Org 1/ Org 2. 

BH3 (Borane) As A Reagent For Hydroboration Of Alkenes (And Alkynes)

Today’s reagent is a staple of Org 1 and the key representative of a genuinely useful process being used every day in laboratories worldwide. It helped secure H.C. Brown the 1979 Nobel Prize (along with Georg Wittig, whose eponymous reaction should be familiar to those in Org 2). I’m talking about BH3 (borane).

drawing-of-borane-bh3-what-it-is-used-for-in-organic-chemistry

Although we commonly just write “BH3” to describe its use in reactions, borane actually doesn’t generally exist as BH3 per se. If you recall that boron only has 3 valence electrons, this means that any neutral compound of boron will lack a full octet and therefore be Lewis acidic (i.e. able to accept a pair of electrons). Two molecules of BH3 tend to associate with themselves in an interaction I’ve heard crudely described by the formula “x = 70-1” , giving B2H6.  Alternatively BH3 readily forms stable compounds with Lewis bases such as tetrahydrofuran (THF) and dimethyl sulfide among others. So it’s quite possible that you’ll see BH3 in these forms as well. It all amounts to the same thing for our purposes. Finally, there are other “boranes” such as disiamylborane- in which one or more of the hydrogens is replaced by an alkyl group. These can also perform the hydroboration of alkenes and alkynes.

Hydroboration of Alkenes And Alkynes

The most important use of BH3 is for the hydroboration of alkenes and alkynes.

use-of-bh3-in-the-hydroboration-of-alkenes-and-alkynes

For the reaction of alkenes, there are two important things to keep in mind. The reaction is selective for the less substituted alcohol (regioselective). This is usually referred to as “anti-Markovnikoff” selective. Furthermore, the reaction always produces the product where the new H and OH are syn to each other (stereospecific).

The reaction of BH3 with alkynes always throws people off. The oxygen still ends up on the less substituted carbon, but  now it looks like not one but two C-C double bonds have disappeared! This is usually the first introduction to the concept of “tautomerism“, and causes a fair amount of angst. In fact, BH3 *did* only add to one C-C multiple bond, but the product has just adopted a different form (More below).

This ‘anti-Markovnikoff” selectivity issue with BH3 causes a lot of stress too. It actually involves no new concepts! This has come up before, in “the most annoying exceptions in org 1“.

Hydroboration: How It Works

Take a “Markovnikoff” selective reaction like the addition of HCl to an alkene. Which is more electronegative, H or Cl?. Cl is (Cl: 3.2, H: 2.2). The more electronegative element lines up with the more substituted end of the double bond.

BH3 is weird because it’s actually the H which is more electronegative! (H: 2.2, B:2.0). Therefore, since H is more electronegative it actually ends up on the more substituted carbon.

mechanism-of-bh3-in-the-hydroboration-of-alkenes

Note that hydroboration can happen up to 3 times with BH3, since there are 3 B-H bonds. Here I’m only going to show it doing one hydroboration, but the exact same steps apply for subsequent hydroborations.

Another thing which throws people off about hydroboration is drawing out the mechanism for going from the hydroboration product to the alcohol.  There are a lot of moving parts here, it is true.

One key point to remember: the OH goes exactly where the boron was, without changing the stereochemistry.

mechanism-for-hydroboration-of-alkenes-with-bh3-oxidation-step.

The two reagents added (NaOH and H2O2) each play a vital role. There are 4 steps.

1)  In the first step, NaOH removes a proton from H2O2, which makes it a better nucleophile.

2) The resulting conjugate base of H2O2 then attacks boron.

3) This sets up the third – key – step, which is rearrangement – shifting of the C-B bond to form a C-O bond, breaking the weak O-O bond in the process. In the third step, OH attacks the boron, which releases the negatively charged alcohol (called an alkoxide). A lot of people have a hard time drawing this when they start out. Don’t forget to draw the ugly version first.

4) Finally, protonation of this with water leads to formation of the neutral alcohol.

How it works: alkynes

BH3 can also be used for the hydroboration of alkynes. To keep things simple, you can follow the example below, but for many purposes BH3 is instead replaced by the bulkier boranes disiamylborane or 9-BBN. The reason is twofold; first, the bulkier reagents have a stronger preference for the less substituted carbon of the alkyne, and furthermore BH3 can perform two hydroborations of the alkyne. See: Hydroboration of Alkynes

mechanism-for-hydroboration-of-alkynes-with-bh3-keto-enol-form

In the reaction of alkynes, the 4 steps are the same. The difference is that the alcohol formed – half alkene, half alcohol (hence enol) is in equilibrium with a constitutional isomer – the aldehyde. This relationship is called keto-enol tautomerism and it comes up a lot in Org 2. In general, keto-enol tautomerism favors the keto (C=O) form by around 5000:1, but this can vary considerably.

P.S. You can read about the chemistry of BH3 and more than 80 other reagents in undergraduate organic chemistry in the “Organic Chemistry Reagent Guide”, available here as a downloadable PDF.

 


(Advanced) References and Further Reading

  1. First example
    CONVENIENT NEW PROCEDURES FOR THE HYDROBORATION OF OLEFINS
    Herbert C. Brown and George Zweifel
    Journal of the American Chemical Society 1959 81 (15), 4106-4107
    DOI:1021/ja01524a071
    Early paper by Nobel Laureate H. C. Brown, describing variants of the classic hydroboration reaction.
  2. Mechanistic studies
    XXIV. Directive Effects in the Hydroboration of Some Substituted Styrenes
    Herbert C. Brown and Richard L. Sharp
    Journal of the American Chemical Society 1966 88 (24), 5851-5854
    DOI: 10.1021/ja00976a029
    A very nice Physical Organic study of the hydroboration of styrenes, involving a Hammett plot (a classic tool in physical organic chemistry) to determine a relationship between the stereochemistry of the reaction and the electron density of the alkene.
  3. References from Organic Syntheses
    A SIMPLE AND CONVENIENT METHOD FOR THE OXIDATION OF ORGANOBORANES USING SODIUM PERBORATE: (+)-ISOPINOCAMPHEOL
    George W. Kabalka, John T. Maddox, Timothy Shoup, and Karla R. Bowers
    Organic Syntheses, Coll. Vol. 9, p.522 (1998); Vol. 73, p.116 (1996)
    DOI : 15227/orgsyn.073.0116
    A Hydroboration-oxidation procedure where the oxidizing agent is sodium perborate, a cheap, safe, easily handled oxidant commonly used in laundry detergents.
  4. Modern Example
    Hydroboration with Pyridine Borane at Room Temperature
    Julia M. Clay and and Edwin Vedejs
    Journal of the American Chemical Society 2005 127 (16), 5766-5767
    DOI: 1021/ja043743j
    A modern method for doing hydroboration at room temperature using pyridine-borane, which usually requires heating to 75-100 °C to liberate the borane.

Comments

Comment section

8 thoughts on “Reagent Friday: BH3 (Borane)

  1. Why don’t you mention the use of borane to reduce carboxylic acids to alcohols? It is important because borane selectively reduces the acid over other groups such as esters. I would be more inclined to buy your reagent guide if it was more complete and mentioned stuff like this :-)

    1. It wasn’t mentioned because it’s often not covered in introductory classes. If you’re looking for more advanced material there are many great resources out there – SANROS and the Portable Chemists’ Companion to name just two.

  2. In the oxidation step of the reaction, why does the hydroxide ion attack the boron, to form the alkoxide? Isn’t the alkoxide a slightly stronger base than the hydroxide?

    Thank you

  3. Pls tell me about reactions of disiamyl borane with alkene which results into formation of aldehyde.
    Thanks

    1. I think you mean, alkyne. Disiamyl borane is a disubstituted borane which does one hydroboration, and the steric bulk of the siamyl groups means that it has an even greater preference for formation of the anti-markovnikov product from an alkyne than BH3. Oxidation of the resulting vinyl borane gives an enol, which , through a process known as tautomerization, gives the aldehyde.

  4. What does the reaction of borane-thf and water look like? For our hydroboration-oxidation lab we had to dry our glassware and I suppose it is because borane-tetrahydrofuran would react with water molecules. Will you indulge me with a mechanism for this reaction in response?

  5. What happens if the borane reacts with a nonterminal alkyne? does a ketone form instead of an aldehyde?

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