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DOI: 10.1055/sos-SD-043-00002

Hirsch, A.; Vostrowsky, O.Science of Synthesis, (20084344.

In 1962 Hay enunciated a homocoupling approach to alka-1,3-diynes 18 in which oxygen is passed through a solution of an alkyne 17 and copper(I) chloride in a complex-forming solvent such as pyridine, and in the presence of catalytic amounts of the bidentate ligand N,N,N,N-tetramethylethylenediamine (Table 3).[‌110‌] As a result, soluble complexes are formed with the intermediate copper(I) acetylides and their reactivity is enhanced. This type of coupling tolerates a wide variety of groups and allows the syntheses of numerous functionalized aliphatic and aromatic alka-1,3-diynes. Adding a small amount of the base 1,8-diazabicyclo[5.4.0]undec-7-ene accelerates the reaction rate,[‌111‌,‌112‌] and it is also advantageous to use 1,2-dimethoxyethane as the solvent.[‌113‌] However, 1,2-dichlorobenzene appears to be a superior solvent for the oxidative polymerization of nona-1,8-diyne under Hay's conditions.[‌114‌] The silyl-protected, resorcinol end-capped buta-1,3-diyne (entry 1) can also be synthesized in 91% yield by homocoupling under Hay conditions.[‌12‌] Moreover, using copper(I) iodide instead of copper(I) chloride, the symmetrically N,N-disubstituted buta-1,3-diyne-1,4-diylbis(4-toluenesulfonamides) (entries 2 and 3) are obtained by the dimerization of the appropriate N-aryl- or N-alkyl-N-tosylethynamides.[‌115‌] Terminal alkynes undergo smooth oxidative coupling in the presence of the copper(I) chloride/N,N,N,N-tetramethylethylenediamine catalytic system in the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [(bmim)PF6] under aerobic conditions.[‌116‌] Thus, a number of alkylacetylenes are obtained from phenylacetylene in yields of 8595%, including symmetrically substituted alka-1,3-diynes (entries 4 and 5). This procedure is also employed for the dimerization of ethynylated thiophenes to afford 1,4-bis(4-thien-2-yl)buta-1,3-diyne (entry 6) as well as a homologous series of bis(oligothienyl)buta-1,3-diynes that may subsequently be transformed into the corresponding conjugated oligothiophenes containing up to eleven repeating units.[‌117‌] The terminally protected compound 1,4-bis(triisopropylsilyl)buta-1,3-diyne is also prepared by Hay oxidative coupling.[‌118‌] A monoprotected dibromoenediyne, used as a FritschButtenbergWiechell rearrangement precursor (see Section, is coupled under Hay conditions to form a tetrabromo dual FritschButtenbergWiechell rearrangement precursor (entry 7) as the only isolable product in 55% yield. The subsequent dual rearrangement provides a conjugated hexayne.[‌119‌] To complete a similar 20-carbon decayne framework, the system can be extended to a tetrabromo dual FritschButtenbergWiechell rearrangement precursor,[‌119‌] which is similarly coupled to the corresponding 3,6,11,14-tetrakis(dibromomethylene)hexadeca-1,4,7,9,12,15-hexayne (entry 8).[‌120‌] A dimer (entry 9) with an iso-poly(triacetylene) backbone is constructed in 48% yield from 5-ethynyl-6-methyl-1-(triisopropylsilyl)hept-5-ene-1,3-diyne by oxidative acetylenic homocoupling.[‌121‌] The preparation of the tert-butyl ether (entry 10) and the 1-adamantyl ether (entry 11) of buta-1,3-diyne-1,4-diol[‌122‌] and that of 1,6-di-1-naphthylhexa-2,4-diyne-1,6-diol (entry 12)[‌123‌] have also all been described.

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