8. (a) Buskuhl H, Freitas RA, Monache FD, Barison A, Campos FR, Corilo YE, Eberlin MN, Biavatti
MW. J. Braz. Chem. Soc. 2009; 20: 1327-1333. (b) Pollo LAE, Bosi CF, Leite AS, Rigotto C, Kratz J,
Simões CMO, Fonseca DEP, Coimbra D, Caramori G, Nepel A, Campos FR, Barison A, Biavatti MW.
Phytochemistry 2013; 95: 375-383.
9. Klein JB, Nowill AE, Franchi JR GC, Biavatti MW, Quintão NLM, Freitas RA. Basic Clin. Pharm.
2013; 113: 307-315.
10. For reviews on the synthesis of polyacetylenes, see (a) Siemsen P, Livingston RC, Diederich F.
Angew. Chem. Int. Ed, 2000; 39: 2632-2657. (b) Shi Shun, ALK, Tykwinski, RR. Angew. Chem. Int.
Ed, 2006; 45: 1034-1057.
11. (a) Sindhu KS, Thankachan AP, Sajitha PS, Anilkumar G. Org. Biomol. Chem. 2015; 13: 6891-
6905. (b) Shi, W. Curr. Organocatal. 2015; 2: 2-13.
12. Cadiot P, Chodkiewicz W. In Chemistry of Acetylenes; Viehe, H. G., Ed.; Marcel Dekker: New
York, 1969; pp. 597-647.
13. Luu T, Tykwinski RR. J. Org. Chem. 2006; 71: 8982-8985.
14. For a review, see Eisler, S, Tykwinski, RR In Acetylene Chemistry. Chemistry, Biology, and
Material Science; Diederich, F, Stang, PJ, Tykwinski, RR, Eds.; Wiley VCH: Weinheim, 2005, pp
259-302.
15. Prévost S, Meier J, Chodkiewicz W, Cadiot P, Willemart A. Bull. Soc. Chim. Fr. 1961; 2171-2175.
16. Bew R E, Chapman JR, Jones Sir ERH, Lowe G J. Chem Soc. C 1966; 129-135.
17. Bartko S, Deng J, Danheiser RL. Org. Synth. 2016; 93: 245-262.
18. (a) Suffert J; Toussaint D. J. Org. Chem. 1995; 60: 3550-3553. (b) Toussaint D; Suffert, J. Org.
Synth. 1999; 76: 214-220.
19. Hofmeister H, Annen K, Laurent H, Wiechert R. Angew. Chem. Int. Ed. 1984; 23: 727-729.
20. Rubin Y, Lin SS, Knobler CB, Anthony J, Boldi AM, Diederich F. J. Am. Chem. Soc. 1991; 113:
6943-6949.
21. Hwang S, Kang HR, Kim S. Org. Synth. 2009; 86: 225-235.
22. 7-(Triisopropylsilyl)hepta-4,6-diyn-1-ol (11): yellowish oil; 1H NMR (400 MHz; CDCl3): 3.76 (t, J
13
= 6.2 Hz, 2H), 2.43 (t, J = 7.0 Hz, 2H); 1.80 (m, 2H); 1.60 (brs, 1H); 1.09 (d, J = 1.3 Hz, 21H). C
NMR (100 MHz, CDCl3) δ 89.8, 80.4, 77.8, 66.3, 61.3, 30.7, 18.5, 15.7, 11.2. HRMS (ESI) m/z
[M+H]+: calculated for C16H28OSi 265.1982; founded 265.1977.
23. For previous syntheses of this alcohol, see refs 5, 15, 16, and (a) Kawanami H, Okada S, Matsuda
H, Doi T, Kikuchi N, Hayamizu K, Oikaw H, Nakanishi H. Mol. Cryst. Liq. Cryst. 1994; 255: 103. (b)
Wang KP, Cho EJ, Yun SY, Rhee JY, Lee D. Tetrahedron 2013; 69: 9105
1
24. Hepta-4,6-diyn-1-ol (6): brown oil; H NMR (400 MHz; CDCl3): δ 3.75 (t, J = 6.1 Hz, 2H), 2.40
(dt, J = 7.0 Hz, J = 1.2 Hz, 2H), 1.97 (t, J = 1.2 Hz, 1H), 1.79 (m, 2H), 1.64 (br s, 1H). 13C NMR (100
MHz, CDCl3) δ 78.2, 68.9, 65.8, 65.4, 61.9, 31.3, 16.2.
25. Procedure for Cadiot-Chodkiewicz cross-coupling to generate deca-4,6,8-triyn-1-ol (1): A 25-mL,
two-necked, round bottomed flask equipped with two rubber septa, a nitrogen inlet needle, and a
magnetic stir bar was charged with degassed aqueous 30% n-BuNH2 solution(5 mL), CuCl (0.028 g;
0.277 mmol; 10 mol%) and NH2OH.HCl (0.192 g; 2.77 mmol; 1 equiv). The reaction mixture was
cooled to 0 °C (with stirring) and the color changed from blue to colorless within seconds, indicating
reduction of Cu(II) to Cu(I). A solution of the terminal diyne 6 (0.300 g; 2.77 mmol; 1 equiv) in 3 mL
of 1:1 (v/v) CH2Cl2/MeOH was added dropwise via cannula over ca. 4 min followed by a solution of
1-iodopropyne (0.922 g; 5.55 mmol; 2 equiv) in 3 mL of 1:1 (v/v) CH2Cl2/MeOH which was added
dropwise via cannula over 4 min. The resulting mixture was stirred at 0 °C until TLC analysis
9