Alkene Reactions

By James Ashenhurst

Hydroboration – Oxidation of Alkenes

Last updated: November 28th, 2022 |

Hydroboration – Oxidation of Alkenes

So far in this series on alkenes, we’ve gone through two families of mechanism pathways. In the carbocation pathway, we saw reactions that proceed with “Markovnikov” regioselectivity, a mixture of “syn” and “anti” stereochemistry, and can be accompanied by rearrangements.  In the 3 membered ring pathway, the regiochemistry is also “Markovnikov”, the stereochemistry is trans (anti), and the reaction proceeds through a 3 membered ring intermediate.

We’ve met at least a dozen different alkene reactions that can fit into these families so far.

Now, along comes a reaction that doesn’t fit any pattern we’ve seen before.

Table of Contents

  1. Hydroboration of Alkenes: Hydrogen Is Added To The “More Substituted” End Of The Carbon (“anti-Markovnikov”) And The Stereoselectivity Is “Syn”
  2. In Hydroboration, No Rearrangements Are Observed, And Neither Is Trapping By Solvent
  3. With An Excess Of Alkene, Multiple Hydroborations Can Occur
  4. Electron Withdrawing Substituents Erode “Anti-Markovnikov” Hydroboration Regioselectivity
  5. The Resulting Organoboranes Are Easily Oxidized To Alcohols With Basic Hydrogen Peroxide
  6. Notes
  7. (Advanced) References and Further Reading

1. Hydroboration of Alkenes: Hydrogen Is Added To The “More Substituted” End Of The Carbon (“anti-Markovnikov”) And The Stereoselectivity Is “Syn”

In the mid 1950’s, H.C. Brown and B. Subba Rao were investigating the use of boron hydrides as reducing agents. When performing the reduction of an unsaturated ester (ethyl oleate) with NaBH4 and catalytic AlCl3 , Subba Rao observed that an excess number of mole equivalents of boron hydride were consumed: 2.37 ( vs. 2.00 for the reaction of saturated ethyl stearate) . Upon further investigation it was found that B-H was in fact adding to the alkene, in a reaction that subsequently became known as “hydroboration”.

It was subsequently determined that borane (which exists natively as B2H6, simplified here as “BH3“) adds to alkenes with the following pattern:

hydroboration of alkenes with bh3 gives anti markovnikov product with syn stereochemistry no rearrangements

Note that the hydrogen is adding to the more substituted end of the carbon (“anti-Markovnikov”) and the stereochemistry is syn.

2. In Hydroboration, No Rearrangements Are Observed, And Neither Is Trapping By Solvent

This doesn’t fit with any of the patterns we’ve seen before! 

That means it’s likely going through a different mechanism!

Of interest is the observation that no rearrangements are observed, even in strained molecules such as pinene:

hydroboration of pinene with bh3 gives new borane with no rearrangement

Furthermore, trapping by solvent is not observed (actually protic solvents are generally a bad idea for hydroboration, as they lead to formation of hydrogen gas and destruction of borane itself).

3. With An Excess Of Alkene, Multiple Hydroborations Can Occur

Interestingly if we add an excess of alkene, we can observe multiple hydroborations. If presented with sufficient alkene, for example, BH3 can perform three additions to alkenes.

hydroboration of alkenes with bh3 can lead to three hydroborations occurring eg methylcyclohexene

4. Electron Withdrawing Substituents Erode “Anti-Markovnikov” Regioselectivity

Here’s another interesting observation. Selectivity for the “anti-Markovnikov” product is very high for propene (94:6). However, when electron withdrawing substituents are added to the alkene, the selectivity for the “anti-Markovnikov” product drops to 74:26. Whatever is responsible for the anti-Markovnikov selectivity must also explain this observation! [Ref]

hydroboration of alkenes with electron withdrawing groups affects anti markovnikov selectivity

5. The Resulting Organoboranes Are Easily Oxidized To Alcohols With Basic Hydrogen Peroxide

Finally, it is of interest that organoborane compounds are not particularly stable under atmospheric conditions (they tend to react with oxygen, burning with a beautiful green flame). However, they can be easily converted to alcohols, which are extremely valuable compounds. The transformation of organoboranes to alcohols can be performed by treating them with basic hydrogen peroxide.

This process is called “hydroboration-oxidation”. Note how the stereochemistry of the C-B bond is preserved in the C-O bond.

hydroboration oxidation of alkenes leads to syn product and preservation of stereochemistry

How might we explain all these observations? Chew on them for a bit and we’ll go through a proposed mechanism next time.

NEXT POST: Hydroboration of Alkenes – The Mechanism


Note 1.  I recall one of my undergraduate instructors, (Prof. Walter Szarek) telling a story about how Brown ended up as a boron chemist due to the fact that his wife gave him a book on boron compounds. I was delighted to find the full story in Brown’s Nobel Lecture:

I received the Assoc. Sci. degree from Wright Junior College (Chicago) in 1935 and the B.S. degree from the University of Chicago in 1936. Why did I decide to undertake my doctorate research in the exotic field of boron hydrides? As it happened, my girl friend, Sarah Baylen, soon to become my wife, presented me with a graduation gift, Alfred Stock’s book, The Hydrides of Boron and Silicon. I read this book and became interested in the subject. How did it happen that she selected this particular book? This was the time of the Depression. none of us had much money. It appears that she selected as her gift the most economical chemistry book ($2.06) available in the University of Chicago bookstore. Such are the developments that can shape a career!

Note 2. Another neat feature of this reaction, not treated in detail here, is that hydroboration is reversible; heating of the organoborane can result in reversion to borane and alkene, and subsequent hydroboration. In such a way can organoborane compounds isomerize, provided there is a sufficient driving force.

(Advanced) References and Further Reading

  1. First example
    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.
    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. 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.
  5. Organoboron halides. Part VI. Hydroboration of 3,3,3-trifluoropropene
    Phillips J.R.; Stone, F.G.A.
    J. Chem. Soc. 1962, 94
    DOI: 10.1039/JR9620000094


Comment section

6 thoughts on “Hydroboration – Oxidation of Alkenes

  1. As usual, great post, but:

    – “hydrogen is adding to the less substituted end of the carbon (“anti-Markovnikov”)” – shouldn’t that be “more substituted”?
    – figure 1: “H and B add to opposite faces of alkene” – shouldn’t it be “the same face”, since the stereochemistry is syn?

    1. The more electron rich double bond would react preferentially, although I would imagine in a mixture, and if diborane were in excess, it would hydroborate every double bond. This is for carbon-carbon double bonds. Heterogeneous double bonds may not react with BH3 if they are electron deficient, at least not without a catalyst (for example a nitro group) or in general react very slowly (like an acid chloride).

      This is because BH3 is an “electrophilic” reducing agent. With only three valence electrons, it’s both planar and its octet is not full. An unfilled octet means it has an open orbital for electrons to come in, and being planar makes it easy for such electrons to approach. This is why it adds to alkenes: the pi bond in a double bond has two accessible electrons to fill the empty BH3 orbital. An electron deficient moiety will not have electrons easily available to give to BH3, so BH3 adds slowly or requires a catalyst.

      Contrast this with NaBH4, which is a “nucleophilic” reducing agent. The boron’s octet is full; there’s no empty orbital to fill by attack from external electrons. However, here the B-H bond is polarized with electrons toward hydrogen, allowing hydrogen to add as a nucleophlic hydride, instead of boron as in the electrophilic case. It’s not a strong reducing agent and won’t reduce many types of double bonds, but with the right alkali metal (Na < Li < Mg < Al), the reducing power of the nucleophilic hydride increases. So-called borohydrides can selectively reduce double bonds based on its reducing power. That selectivity is very useful when you want to target a specific double bond without affecting another double bond in the same molecule.

  2. A great joke in the paper from Brown for receiving the nobel prize:

    “My parents were far-seeing in giving me the initials H.C.B.”

    made directly below the reaction for hydroboration ;)

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