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Hirsch, A.; Vostrowsky, O., Science of Synthesis, (2008) 43, 44.
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 85–95%, 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 Fritsch–Buttenberg–Wiechell rearrangement precursor (see Section 43.1.1.1.17), is coupled under Hay conditions to form a tetrabromo dual Fritsch–Buttenberg–Wiechell 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 Fritsch–Buttenberg–Wiechell 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.
Meeee 8 Meeeeeeeeee Meeeeeeeeeee ee eee Mee Meeeeeee Meeeeeeee[88,888–888,888–888]
Meeee | M8 | Meeeeeeeeee | Meeee (%) | Mee |
---|---|---|---|---|
8 | ![]() |
MeMe, MMMMM, M8, eeeeeee, 88°M | 88 | [88] |
8 | MMeMe | MeM, MMMMM, M8, eeeeeee, ee, 8 e | 88 | [888] |
8 | MMeMe | MeM, MMMMM, M8, eeeeeee, ee, 8 e | 88e | [888] |
8 | (MM8)8Me | MeMe, MMMMM, M8, [eeee]MM8, 8 e | 88 | [888] |
8 | MM8MMe | MeMe, MMMMM, M8, [eeee]MM8, 8.8 e | 88 | [888] |
8 | ![]() |
MeMe, MMMMM, MeMM, MM8Me8 | 88e | [888] |
8 | ![]() |
MeMe, MMMMM, MM8Me8 | 88 | [888] |
8 | ![]() |
MeMe, MMMMM, MM8Me8 | 88 | [888] |
8 | ![]() |
MeM, MMMMM, M8, MM8Me8, ee | 88 | [888] |
88 | Me-Me | MeM, MMMMM, M8, eeeeeee, 88–88 eee, ee | 88 | [888] |
88 | ![]() |
MeM, MMMMM, M8, eeeeeee, 88–88 eee, ee | 88 | [888] |
88 | ![]() |
MeMe, MMMMM, M8, eeeeeee, 8 e, ee, eeee 88°M, 8 e | –e | [888] |
e [eeee]MM8 = 8-eeeee-8-eeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeee.
e ee 888–888°M (eee).
e ee 88–88°M.
e Meeee eee eeeeeeee.
Meeeeeeee eee eeeeeeee eeee ee eee-eeeeee eeee(eeeeeeeeeeee) (MMM) eeeeeeee eeeeeee e eeee-8,8-eeeee eeeeeeeeeeeee eeee eee eee eeeeeee eeeeeeee ee eeeeeeeee Mee eeeeeeeeeeeeee ee eeeeee eeeee eeeeeeeeeee eeeee-8,8-eeeeeeeeeeee-8-eee-8,8-eeeee ee eee-8-eee-8,8-eeeee. Meeeeeeeeee ee eeee eeeee eeeeeee e eeeeee eeeee ee π-eeeeeeeeee eeeeeeee eeeeee eee eee eeeeeee eeeeeeeeeeee ee eeeee eeeeeeeee eee eeeeeeee eeee eeeeee-eeee eeeeeeeeee eeeeeeeee.[88] Meeeeeee eeee eeeeeeee eeeeeeee, eeeeeee eee-eeeeee eeee(eeeeeeeeeeee) eeeeeeee 88–88 eee eee eeeeeeeee 88 eee 88 eee eeeeeeee ee e eeeeeeeeeee eeeeeeeeeeee–eeeeeeeee Mee eeeeeeeeeeeeeee eeeeeeee eeeee eee-eeeeeee eeeeeeeeee (Meeeee 8).[888–888] Meeeeeeeeeee eeeeeeeee ee eeee eeee eee eeeeeeee ee ee eeeeeeeee eee eeeeeeeeeeeee eeeeeeeeee eeeeeeeeeeeeeee eeeeeeee eeeeeeee eeee eeeeeee eeeeeeeee eeeeeeeee eeeeee ee eeeee “eeeee-eeeeeeee”.[888] Meee eeeeeeeee eeeee eeeee ee eeeeee eee eeeeeeee eee eee eee ee eeeeee-eeeee eeeeeeeee eeeee ee eeeeeeeee eeeeeeeeeee eee eeeeeeeeeeeee eeeeeee.
Meeeee 8 Meee(eeeeeeeeeeee) Meeeeeee eee Meeeeeeee eeee Mee Meeeeeeeeeeeeee[888–888]
Meeeee e eeeee ee eee eeeeeeeee ee eeeeeeee, eeeeeeeeee ee eeeeeeee-eeeeee eeeeeeeee eee-eeee, ee eee eeeeeeee ee eeeeeee eee eeeeeeeee ee eee eeeeeeeeeeeee eeeee-eeeeeee eeeeeeee 88 (M8 = MMMMM) ee 88 (M8 = MMMM) ee 88 eee 88% eeeeee, eeeeeeeeeeee, ee eeeeeeeee eee eeeeeeeeeee eeeeeeee eeeeeeeee 88 eeee ee eeeeee ee (eeeeeeeeeeeeee)eeeeeeeee eee eeeeee eee Mee eeeeeeee ee eeeee eeeeeeee.[88] Meeee eeeeeeeee eee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeee eeeeeeee 88 (M8 = MMMMM) eee 88 (M8 = MMMM) ee eeeeee ee 88 eee 88%, eeeeeeeeeeee. Meeee eeeeeee eeeeeeeeee eee eeeeeeeeee ee eeee ee eee eee eeeeeeee eeeeee eeeeeeeee ee eee eeeeeeee 88 ee eeeeeeee ee eeeee eeeeeeee eeee ee eeeeee ee (eeeeeeeeeeeeee)eeeeeeeee eee eeee eeeeeee eee eeeeeeeee 88 ee eeeeee ee 88–88% (Meeeee 8).[888]
Meeeee 8 Meeeeeeeeeeee Meee-8,8-eeeeee ee Meeee Meeeeeee eeeee Mee'e Meeeeeeeee[88,888]
Mee eeeeeeee eeeeeee 88 ee eeeeeeee ee eee eeeee eeeeeeee ee eee eeeeeeee eeeeeeee 88 eeee (eeeeeeeeeeeeee)eeeeeeeee eeeee Mee'e eeeeeeeeee (Meeeee 8); ee eee eeee ee eeee ee eee eeeeeee eeee eeee eee e eeeeeeeee eeeeeeeeeeee ee eee-eeee(eeeeeeeeeeeee) (eee-MMMe).[888]
Meeeee 8 Meeeeeeee ee 8-Meeeeeeeeeeeee-8,8-eee(eeeeeeeeeeeeee)eeee-8,8,8,8-eeeeeeee ee Meeee Meeeeeee eeeee Mee'e Meeeeeeeee[888]
Meeeeeeeeeee Meeeeeeee
Meee-8,8-eeeee-8,8-eeeeeee(8-eeeeeeeeeeeeeeeeeee) (Meeee 8, Meeeeee 8 eee 8); Meeeeee Meeeeeeee:[888]
MMMMM (8 μM, 8.888 eeee) eee eeeee ee ee ee e eeeeeeeeee ee MeM (8 ee, 8.888 eeee) ee eee eeeeeee (8 eM) eeeeeeeee eeeee M8. Meeee 88 eee, e eeee ee eee eeeeeeeeeee eeeeee (8.888 eeee) ee eeeeeee (8 eM) eee eeeee, eee eee eeeeeee eee eeee eeeeeeeeee eeeeeee eee e eeeeeee 8 e ee eeeee eee eee eeeeeeee eeeeeeee eee eeeeeeeeeee (MMM). Meeee eeeeeee ee eee eeeeeee, eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 8:8).
8,88-Mee{8-eeee-eeeee-8-[8-(eeeeeeeeeeeeee)eeee-8,8-eeeeee]eeeeeee}eeeeeeee (88, e = 8); Meeeeee Meeeeeeee:[888]
MeMe (8.88 e, 88.88 eeee) eee MMMMM (8.88 ee, 8.88 eeee) eeee eeeeeeeee ee eeeeeee (888 eM) eee eee eeee eee eeeeeee eee 88 eee. Me eee eeee eeeeeeee eeeeeee eeeee, eee eeee eeee eee eeeeee eeeeeeee eeee eeeeee eeee eeeeeee (8 eM). Mee eeeeeeee eeee eeeee eeeeeeee eee eeeeeeee eeee eeeee eeeeeeee (eeee 88 eee) ee e eeee ee (eeeeeeeeeeeeee)eeeeeeeee (8.88 e, 88.88 eeee) eee eee eeeeeee 88 (e = 8; 8.88 e, 8.88 eeee) ee eeeeeee (888 eM). M8 eee eeeeeee eeeeeeeeeeee eee 88 eee eeeeeee eee eeee ee eeeee eeeeeeeeee ee eeeeeee eeee eeeee ee eeeee ee eeeeeee eeeeeeeeee. Meeeeeee (MMM, eeeeee eee, MM8Me8/eeeeee 8:8) eeeeee eeee eee eeeeeeee eeeeeeee 88 (e = 8) eeeee eeeeeeee ee eeeee eeeeeeeeee eeeeeeee ee (eeeeeeeeeeeeee)eeeeeeeee (8 × 88 ee eee 8 × 888 ee) eeee eeeee ee eeee eee, eeeee eeeeeeee eee eeeeeee eee 88 e, 88% MMe (888 eM), M8M (888 eM), eee eeeeee (888 eM) eeee eeeeeeeeee. Mee eee eeeeee eeee eee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee eeeeee (8 × 888 eM). Mee eeeeeeee eeeeee eeeeeeee eeee eeeeee eeeeeeeeeeee eeee 88% MMe (888 eM) eee M8M (8 × 888 eM), eee eeeee (Me8MM8). Meee eee eeeeeee eee eeee eeeeeee, eee eeeee eeeeeeee eee eeeeeeee eeee eee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeeeeeeee 8:8) ee e eeeeeeeee eeeee; eeeee: 888 ee (88%).
References
[12] | Meeeeee, M.; Meeeee, M.; Meeeeeeeeeee, M.-M.; Meeeee, M., Meee.–Mee. M., (8888) 8, 888. |
[24] | Meeeeeeee, M., Meee. Meeeee. (Meeeeeeee), (8888), 888. |
[110] | Mee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[111] | Meeeeeee, M., Meeeeeeeeee Meeeeeeeee Meeeeeeee, 8ee ee., Meeeeeee: Meeeeeeee, (8888); ee 888–888. |
[112] | Meeeeeeeee, M. M.; Meeeeeeeeee, M. M.; Meeeeeee, M., Meee. Meee. Meee. Meee-Mee, (8888) 888, 888. |
[113] | Meeeeeeee, M.; Müeee, M., Meeeeeeeeee Meee., (8888), 8888. |
[114] | Meee, M. M.; eee Meeeeee, M. M.; Meeeee, M.; Meeeeee, M. M., Meeee. Meeeee., (8888) 88, 88. |
[115] | Meeeeeeee, M.; Meeeeee, M.; Meá, M., Meeeeee, (8888), 888. |
[116] | Meeee, M. M.; Meeee, M. M. M.; Meeee, M. M.; Meeeeeee, M. M.; Meeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[117] | Meöeee, M.; Mäeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[118] | Meeeeeý, M.; Meeee, M.; Meeešee, M., Meeeee, (8888) 88, 888. |
[119] | Meeeee, M.; Meeeee, M.; MeMeeeee, M.; Meeeeeeee, M. M., Meee.–Mee. M., (8888) 8, 8888. |
[120] | Meeeee, M.; Meeeeee, M. M.; Meeeeee, M.; Mee, M.; MeMeeeee, M.; Meeeeee, M. M.; Meeeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[121] | Meee, M.; MeMeeeee, M.; Meeeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[122] | Meeeeee, M.; Meeeeàe, M. M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[123] | Meeeeeee, M.; Meeeeee, M.; Meeeee, M.; Meeeeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
[124] | Meeeeeeee, M.; Meeeeeeee, M. M.; Meeeeeeee, M.; Meeeeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeee, M.; Müeeee, M.; Meeeee, M.; Meeeeeeeeeee, M.-M.; Meeee, M.; Meeee, M.; Meeeeeeee, M., Mee. Meeee. (Meeeeeee, Mee.), (8888) 8, 888. |
[125] | Meeeeeeee, M.; Meeeeee, M.; Meeeeeeee, M.; Meeee, M. M.; Meeeee, M.; Meeeeee, M.; Meeeeee, M.; Meeeeeee, M.; Meeeeee, M.; Meeee, M.; Meeeeeee, M.; Müeeee, M.; Meeeeee, M.; Meeee, M. M.; Meeeee, M.; Meeeeeeeeeee, M.-M.; Meeee, M., Mee. Meeee. (Meeeeeee, Mee.), (8888) 8, 888. |
[126] | Meeeee, M. M.; Meeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeeeeeeee, M.-M.; Meeeeeeee, M.; Müeeee, M.; Meeee, M.; Meéeee, M.-M., Meee.–Mee. M., (8888) 8, 8888. |
[127] | Meeeee, M. M.; Meeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeeee, M.; Meeeeeeeeeee, M.-M.; Müeeee, M.; Meeee, M.; Meeeeeeee, M., Meee.–Mee. M., (8888) 8, 8888. |
[128] | Meeeeee, M.; Meeeee, M.; Meeeeeeee, M.; Meeeeeeeeeee, M.-M.; Meeeeeee, M.; Meeee, M.; Meee, M.; Meeeee, M., Meeee. Meee., (8888) 888, 888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 888. |
[129] | Meeee, M. M.; Meeeeee, M.; Meeeeeee, M.; Meeeeee, M. M.; Meeeee, M.; Meeeeeeeeeee, M.-M.; Meeee, M.; Meeeeeeee, M., Meee. Meee. Meee, (8888) 88, 888. |
[130] | Meeeee, M. M.; Mäeee, M.; Meeeeeeee, M., Meeee. Meee., (8888) 888, 888; Meeee. Meee. Mee. Me., (8888) 88, 888. |
[131] | Meeeeeee, M. M.; Meeeeeeee, M. M.; Meeeeeee, M.; Meeeeeeee, M., Meee. Meee. Meee, (8888) 88, 888. |
[132] | Meeeeee, M.; Meeeeeeeee, M.; Meeeee, M., Mee. M. Mee. Meee., (8888), 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8e, 88.
- 8.Meeeee-Meee, (8888) 8/8e, 888.