Reactions of Alkynes from Ch.

14
Jacquie Richardson, Spring 2010 - Page 1 Most of the reactions that alkynes do are directly analogous to the things that alkenes do in chapters 4 & 5. The main difference is that an alkene can only undergo an addition once, turning it from a double bond to a single bond. A triple bond can react up to two times: once to make it go from triple to double, and again to make it go from double to single. So the outcome of the reaction will often depend on how many equivalents of reagents you add to it. For all these reactions, Ill show them occurring on a terminal alkyne: one which has an R group on one side and an H on the other. This is so you can tell what prefers to add where. Many alkynes that youll see, however, have R groups on both ends. In these cases, theres no real preference in regiochemistry, so Markovnikov and anti-Markovnikov cease to have any meaning. Another complication is caused by the keto-enol tautomerism. Any time you have an OH directly attached to an alkene, it will rearrange: H OH H O H H H H H Keto-enol tautomerism There are three parts involved in this rearrangement: you need to switch around the location of the double bond, you need to add an H to the far carbon, and you need to remove an H from the oxygen. The reaction can happen in acidic or basic conditions. The same three steps will happen either way, its just a question of what happens first. In acidic conditions, you have an excess of protons, so the add-a-proton step happens first:
H H H OH H H H H O H H OH2 H H H H O

But in basic conditions theres a lack of available protons, so the remove-a-proton step happens first.
H H O H H OH H H O H H H OH H H H O

1) Reactions that add 2 non-H groups: For alkenes, we covered several different combinations of what to add. The alkynes chapter only looks at one of these: adding two halogens across a bond. The mechanism is pretty much the same as before.
Br 2, CH 2Cl2 (1 equiv) Br 2, CH 2Cl2 (2 equiv) H 3C Br H 3C Br Br Br H Br H Br

Dihalogenation:

H3C

H3C

2) Reactions that add 1 H and 1 non-H: Just like for alkenes, these can be subdivided into those that follow Markovnikovs Rule, and those that dont. a. Markovnikov-style reactions: These are very similar to the ones we covered in Ch. 4. You can add either one or two equivalents of HBr, depending on stoichiometry. If you want to make absolutely sure that all the molecules stop after a single addition, you + can include something like (C2H5)4N Br , although this is not required.

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Jacquie Richardson, Spring 2010 - Page 2

Hydrogen halide addition: H3C

HBr (1 equiv) HBr (2 equiv)

H3C Br H3C Br Br H3C

H H H H H H O H H

H3C

Acid-catalyzed hydration: H3C

H3C HO H H For hydration, you add the OH Markovnikov-style first. As soon as it forms, the enol will rearrange to the ketone. And since youre already in acidic conditions, that will be the mechanism that is followed.
b. Anti-Markovnikov-style reactions: Again, these both use similar reagents to what we used for alkenes. One difference is that, to force stereochemistry to be more selectively anti-Markovnikov and to make sure that only one addition occurs we can use either BH3THF or a more steric version of it, called disiamylborane. H3C Br HBr, ROOR H Radical hydrogen halide addition: H3C (1 equiv) H H H3C Br HBr, ROOR H H H3C H (2 equiv) H Br

H2O, H2SO4 HgSO4

Hydroboration-oxidation: H3C

1) disiamylborane 2) H2O, H2O2, OH-

H3C H

OH H H

CH3 O H H

Once the OH is added anti-Markovnikov style, it will tautomerize to the carbonyl compound in this case, the aldehyde. Since were already using basic conditions to make the enol, the mechanism will be base-catalyzed tautomerization. 3) Reactions that add 2 H: When we were looking at alkenes, there was only one reaction in this category: H2 and Pd/C. Now we know a couple more. CH3 CH3 H2, Pd/C H3 C CH3 Hydrogenation with H H Alkane palladium: H H

Hydrogenation with H3C Lindlar's catalyst:

CH3

H2, Lindlar

H3 C H

CH3 Cis alkene H H Trans alkene H CH3

Reduction with sodium H3C and liquid ammonia:

CH3

Na, NH3(liq)

H3C

Palladium will add as many Hs as it can, to make the alkane. If you want to make it stop partway at the alkene, you have to poison the catalyst with some form of lead or barium. The mechanism for both these solid-phase reactions is the same: its a concerted addition, so each pair of Hs always adds to the same face. Thats why Lindlars catalyst will always give you the cis alkene. For the trans alkene, you need totally different conditions. This reaction takes place in liquid ammonia, with solid sodium metal mixed in with it. This is called a dissolving metal

Reactions of Alkynes from Ch. 14

Jacquie Richardson, Spring 2010 - Page 3 reduction. The mechanism is four steps: Add an electron, add a proton, add an electron, add a proton. It may seem odd that sodium will just give an electron up to the molecule entirely, but remember: any time you have an organometallic species, you can depict it as an ionic bond or a covalent bond both are two extremes of the same spectrum. So in the first step, you could show sodium contributing an electron to form a bond to the molecule, just like the bromine radical did when we were looking at radical halogenation. But in the next step, just like any organometallic, the molecule will be primarily interested in pulling an H from whatever protic source is available. In terms of why it makes the trans form specifically, you should know already that trans alkenes are more stable due to lower sterics. Since this molecule has the opportunity to get itself to either the cis or trans form at any step in the mechanism, it will end up being trans most of the time. As a side note: dont get Na/NH3 confused with NaNH2! They look similar, but in Na/NH3, sodium has a single electron which it can donate to the molecule. In NaNH2, sodium already has a plus charge, so it wont be doing much NH2 will be doing all the work, as a strong base. Na H3 C Na Na H 3C H3C H H NH2 or H3 C CH 3 CH3 CH 3 CH3 Na

H3 C H

H CH3 H 2N H

H 3C

H or CH 3

H 3C Na

H CH 3

4) Reactions that treat the alkyne as a nucleophile, rather than adding across the triple bond: This is something unique to alkynes - alkenes did not do this. It turns out that an H next to a triple bond has a very low pKa for a C-H bond; carbon with a triple bond is much more stable with a minus charge than carbon with a single or double bond. This means we can deprotonate with a sufficiently strong base, typically NaNH2 (sodium amide). This makes an acetylide anion, which is a strong base/good nucleophile. If you remember chapter 9, things in this category will do SN2 on methyl, primary and maybe secondary, and E2 on tertiary. So if we take the acetylide and react it with a suitable alkyl halide, we can stick the two molecules together with SN2.
NaNH 2 CH 3 Br H 3C H H 3C H 3C CH3 This is a great way to form new carbon-carbon bonds, and is very useful in syntheses for putting big sections of the carbon skeleton together.

5) Making alkynes in the first place: This is similar to the way you most often make alkenes: doing an elimination. You need to do it twice, though, once to make the double bond and once to make the triple bond. For each elimination, you need an H and a leaving group on adjacent carbons. Again, the base you use is normally sodium amide. The groups youre about to lose in any given step are circled. The two halogens can be either on the same or different carbons. Only the first elimination is truly E2, although the second elimination is so similar that it often gets called E2 as well. The important difference in outcomes is based on the difference between internal alkynes (those with an R group on either side) and terminal alkynes (those with an H on one side.) In the case of terminal alkynes, the H will come off whether you want it to or not (see section 4 above), so youll automatically chew through a third equivalent of NaNH2. To put the proton + back on at the end, you need a workup with H2O or H3O .

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Jacquie Richardson, Spring 2010 - Page 4
H Br 1st eq. NaNH 2 H Br H H 1st eq. NaNH 2 H Br H Br H 1st eq. NaNH 2 H Br H E2 H 2nd eq. NaNH2 Br "E2" H 3rd eq. NaNH 2 H3 O+ H Br E2 Br 2nd eq. NaNH 2 "E2" H E2 Br 2nd eq. NaNH 2 "E2"