I'm trying to figure out a method to add a linear alkyl chain R and a hydrogen atom H across the triple bond of a terminal alkyne. The alkyl chain should end up on the internal carbon (C-2):

Addition of RH to alkynylcyclobutane

My attempt :

First, we can hydrolyse the alkyne to produce a methyl ketone. Addition of a Grignard reagent produces the tertiary alcohol. But, now I'm stuck as I can't treat it with $\ce{H2SO4}$, because then ring-expansion will ruin the whole matter.

Proposed scheme

How to move on?

  • 1
    $\begingroup$ You want to add R–H across an alkyne? (you need to specify two things for an addition reaction; you can't just add R to one carbon and not do anything to the other carbon, well, unless you're aiming for a radical product. :-) ) $\endgroup$ Jul 8, 2020 at 4:34
  • $\begingroup$ @orthocresol: Yes, I want to add R-H across an alkyne, directly or indirectly. $\endgroup$ Jul 8, 2020 at 4:57
  • $\begingroup$ Maybe from the ketone make an enol triflate, then do some kind of Pd cross-coupling. But I'm sure you will get better suggestions from others. $\endgroup$ Jul 8, 2020 at 5:27
  • $\begingroup$ @orthocresol: I'll take a look at it (I heard triflates for the first time actually), and thanks for the edit ;) $\endgroup$ Jul 8, 2020 at 5:36
  • 1
    $\begingroup$ The simplest route is to treat the alkyne with RCuMgX2 (Normant, 1976) followed by aqueous work up. Schwartz (Zr) and Negishi (Zr, Ti) methodology is also applicable. $\endgroup$
    – user55119
    Jul 8, 2020 at 16:16

1 Answer 1


Here is a potential solution using old-school chemistry, though with several steps.

  1. Hydroborate the alkyne and work up with $\ce{H2O2}$ to give the aldehyde.

  2. Alkylate the aldehyde enolate with $\ce{RI}$, either directly (LDA or LiHMDS) or via enamine/silyl enol ether

  3. Reduce aldehyde to alcohol ($\ce{NaBH4/EtOH}$)

  4. Form triflate/mesylate and eliminate (DBU/Toluene, reflux)

If you wish to explore @orthocresol's suggestion of enol triflate coupling then coupling the triflate with the cuprate of your alkyl chain looks to be viable according to this Tet. Lett. article from McMurry and Scott1


  1. John E. McMurry, William J. Scott, “A new method of olefin synthesis. Coupling of lithium dialkylcuprates with enol triflates,” Tetrahedron Letters 1980, 21(45), 4313-4316, DOI: 10.1016/S0040-4039(00)77845-2
  • $\begingroup$ This is the better method, which eliminate rearrangement possibilities. $\endgroup$ Jul 8, 2020 at 8:16
  • $\begingroup$ Also, the last step can be achieved by converting alcohol to halide followed by $\mathrm{E2}$ elimination (using $\ce{t-BuK}$). $\endgroup$ Jul 8, 2020 at 8:25
  • 1
    $\begingroup$ Alkylation of primary, saturated halides with enamines does not work well. Stork and Dowd made an improvement by enolizing t-butylimines with Grignard reagents. pubs.acs.org/doi/pdf/10.1021/ja00897a040 $\endgroup$
    – user55119
    Jul 8, 2020 at 16:31

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