Diphenylacetylene

[501-65-5]  · C14H10  · Diphenylacetylene  · (MW 178.24)

(precursor to substituted stilbenes1,2 and benzil;3 participant in cycloaddition chemistry;4 symmetrical p-acidic ligand used widely in organometallic chemistry5)

Physical Data: mp 62.5 °C; bp 90-97 °C/0.3 mmHg; d 0.990 g cm-3.

Solubility: sol ether, hot alcohol.

Form Supplied in: colorless solid; widely available.

Handling, Storage, and Precautions: low oral toxicity; possible danger from absorption through skin.

Introduction.

Due to the symmetry and high degree of planarity of diphenylacetylene, it has enjoyed enormous success as a highly Lewis acidic and sterically accessible alkyne for use in various areas of organic chemistry, as well as in organometallic chemistry where it serves as an excellent ligand of varying hapticity.

Oxidation and Reduction.

The oxidation of diphenylacetylene is reported to proceed under a variety of conditions. Its cleavage to benzoic acid has been accomplished by molybdenum(VI) and tungsten(VI) polyoxometalates,6 as well as by [bis(trifluoroacetoxy)iodo]pentafluorobenzene.7 Chromium-based complexes,3 zinc/chromium,8 electrooxidation,9 and Barium Manganate,10 among others,11 have been successfully utilized in the oxidation of diphenylacetylene to benzil. However, methods for its oxidation to the monoketone are scarce.12

The reduced states of diphenylacetylene are attainable via several efficient methods. (E)-Stilbene is produced in 80% yield with the aid of NiCl2.4PPh3.1 Hydrogenation over a ruthenium catalyst2 provides (Z)-stilbene, as does the use of CoCl2.4PPh3/SmI2/AcOH13 or zinc in combination with Pd/C.14 Reduction of the alkyne bond to the alkane level is achieved with the use of hydrogen and a montmorillonite-(diphenylphosphine)palladium(II) complex,15 or zinc in combination with Pd/C.14

Addition of X-Y Across the Alkyne p-Bond.

Addition across the alkynic bond occurs with a number of reagents. Formal addition of RS-Cl (eq 1),16 PhSe-F,17 Me3Sn-PPh2, PhS-F, PhS-SPh,18 and ClHg-OAc19 proceeds in trans fashion in each instance. However, similar addition of Bu3Sn-H (eq 2),20 RNH-H,21 and HO2C-H22 leads to the formation of cis-stilbene derivatives. H-CN,23 TMS-CN,24 X2 (X = halogen),25 Et-AlEt2,26 and Al-H27 additions to diphenylacetylene have also been reported.

Susceptibility to Carbene Addition.

Diphenylacetylene undergoes addition with chromium, tungsten, and cobalt28 carbenes. Chromium Fischer-type carbenes react with diphenylacetylene to form cyclopentenones (eq 3).29 Pyrrolinones are accessed when nitrogen is present in the chromium carbene reagent (eqs 4 and 5).30 Tungsten carbenes of the Fischer class respond differently in that they form seven-membered rings (eq 6).31 Diphenylacetylene has also demonstrated an ability to undergo facile cycloaddition with ortho-manganated aryl ketones to afford inden-1-ols (eq 7).32

Interaction with Various Metals.

The response of diphenylacetylene to palladium in coupling33 and annulation (eq 8)34 transformations is well documented. Spiroannulation has been effected with the aid of nickel (eq 9),35 and insertion into zirconium complexes has been shown to provide a variety of unsaturated molecules.36 Finally, diphenylacetylene has exhibited a general propensity for ligating to organometallic complexes37 and clusters,38 and to be capable of engaging in metathesis reactions.39

Ring Formation and Cycloaddition.

Incorporation of a vicinal diphenyl group into rings of various types has been demonstrated repeatedly. Oxazoles,40 benzothiophenes,41 indoles,42 pyrroles,43 and furan-2(5H)-ones44 among others45 containing this arrangement have been reported. Ring construction that involves the diphenylacetylene moiety has been accomplished in various ways. Diphenylacetylene undergoes cycloaddition to ketenes of several types, with subsequent fragmentation and rearrangement (eqs 10 and 11).46

Diphenylacetylene participates satisfactorily in Pauson-Khand reactions.47 Furthermore, [3 + 3] cycloaddition with azomethine ylides provides the respective pyrrole in good yield (eq 12).48 Examples of [4 + 2],49 [2 + 2],50 1,3-dipolar,51 and other cycloadditions52 have been widely reported.

Related Reagents.

Dimethyl Acetylenedicarboxylate.


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Jeffrey N. Johnston

The Ohio State University, Columbus, OH, USA



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