9824
S-i. Kawaguchi et al. / Tetrahedron 68 (2012) 9818e9825
(b) Heathcock, C. Comprehensive Organic Synthesis: Selectivity, Strategy and Ef-
CDCl3)
d 14.0, 22.5, 31.0, 31.4, 35.5, 107.7, 126.4, 128.0, 128.2, 139.0,
ficiency in Modern Organic Chemistry; Pergamon: Oxford, UK, 1992; Vol. 2.
2. For recently examples, see: (a) Paterson, I.; Doughty, V. A.; McLeod, M. D.;
Trieselmann, T. Tetrahedron 2011, 67, 10119; (b) Ying, M.; Roush, W. R. Tetra-
hedron 2011, 67, 10274; (c) Domingo, V.; Silva, L.; Dieguez, H. R.; Arteaga, J. F.;
Quilez, J. F.; Barrero, A. F. J. Org. Chem. 2009, 74, 6151.
143.9; MS (EI), m/z (%)¼300 (Mþ, 3), 173 (MþꢁI, 100).
4.3.10. 1-(1-Iodoethenyl)-4-methoxybenzene (3j).5a Colorless oil; 1H
NMR (400 MHz, CDCl3)
d
3.81 (s, 3H), 5.99 (d, J¼1.8 Hz, 1H), 6.37 (d,
3. Kropp, P. J.; Crawford, S. D. J. Org. Chem. 1994, 59, 3102.
4. Ez-Zoubir, M.; Brown, J. A.; Ratovelomanana-Vidal, V.; Michelet, V. J. Organomet.
J¼1.8 Hz, 1H), 6.82 (d, J¼9.2 Hz, 2H), 7.46 (d, J¼8.7 Hz, 2H); 13C NMR
Chem. 2011, 696, 433.
(100 MHz, CDCl3)
d 55.5, 107.4, 113.5, 125.7, 129.5, 134.3, 160.1; MS
(EI), m/z (%)¼260 (Mþ, 3), 133 (MþꢁI, 100).
5. For the synthesis methods of internal iodoalkenes from the corresponding al-
kynes, see: (a) Pross, A.; Sternhell, S. Aust. J. Chem. 1970, 23, 989; (b) Brown, H.
C.; Somayaji, V.; Narasimhan, S. J. Org. Chem. 1984, 49, 4822; (c) Reddy, C. K.;
Periasamy, M. Tetrahedron Lett. 1990, 31, 1919; (d) Kamiya, N.; Chikami, Y.; Ishii,
Y. Synlett 1990, 675; (e) Gao, Y.; Harada, K.; Hata, T.; Urabe, H.; Sato, F. J. Org.
Chem. 1995, 60, 290; (f) Campos, P. J.; García, B.; Rodríguez, M. A. Tetrahedron
Lett. 2002, 43, 6111; (g) Shimizu, M.; Toyoda, T.; Baba, T. Synlett 2005, 2516; (h)
Moleele, S. S.; Michael, J. P.; de Koning, C. B. Tetrahedron 2006, 62, 2831; (i)
Bartoli, G.; Cipolletti, R.; Di Antonio, G.; Giovannini, R.; Lanari, S.; Marcolini, M.;
Marcantoni, E. Org. Biomol. Chem. 2010, 8, 3509; (j) Kawaguchi, S-i.; Ogawa, A.
Org. Lett. 2010, 12, 1893.
4.3.11. 1-Bromo-4-(1-iodoethenyl)benzene (3k).6d Colorless oil; 1H
NMR (400 MHz, CDCl3)
d
6.08 (d, J¼0.9 Hz, 1H), 6.45 (d, J¼1.4 Hz,
1H), 7.36 (d, J¼8.8 Hz, 2H), 7.42 (d, J¼8.9 Hz, 2H); 13C NMR
(100 MHz, CDCl3)
d 105.7, 123.1, 128.0, 129.7, 131.4, 140.7; MS (EI),
m/z (%)¼310 (Mþþ2, 3), 308 (Mþ, 3), 183 (Mþþ2ꢁI, 56), 181 (MþꢁI,
62), 102 (MþꢁIeBr, 100).
6. For the synthesis methods of internal iodoalkenes except the methods from
alkynes, see: (a) Byrd, L. R.; Caserio, M. C. J. Org. Chem. 1972, 37, 3881; (b)
Barton, D. H. ,R.; Bashiardes, G.; Fourrey, J.-L. Tetrahedron Lett. 1983, 24, 1605;
(c) Lee, K.; Wiemer, D. F. Tetrahedron Lett. 1993, 34, 2433; (d) Furrow, M. E.;
Myers, A. G. J. Am. Chem. Soc. 2004, 126, 5436; (e) Krafft, M. E.; Cran, J. W.
Synlett 2005, 1263.
7. For the synthesis methods of E or Z-terminal iodoalkenes, for example, see: (a)
Kluge, A. F.; Untch, K. G.; Fried, J. H. J. Am. Chem. Soc. 1972, 94, 9256; (b) Piers, E.;
Grierson, J. R.; Lau, C. K.; Nagakura, I. Can. J. Chem. 1982, 60, 210; (c) Brown, H.
C.; Subrahmanyam, C.; Hamaoka, T.; Ravindran, N.; Bowman, D. H.; Misumi, S.;
Unni, M. K.; Somayaji, V.; Bhat, N. G. J. Org. Chem. 1989, 54, 6068; (d) Takami, K.;
Mikami, S.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2003, 68,
6627; (e) Huang, Z.; Negishi, E. Org. Lett. 2006, 8, 3675.
8. For the synthesis methods of other iodoalkenes, see: (a) Rahman, M. A.; Kita-
mura, T. Tetrahedron Lett. 2009, 50, 4759; (b) Li, M.-M.; Zhang, Q.; Yue, H.-L.;
Ma, L.; Ji, J.-X. Tetrahedron Lett. 2012, 53, 317.
9. For the hydroiodination of activated alkynes by using iodide anion, see: (a)
Taniguchi, M.; Kobayashi, S.; Nakagawa, M.; Hino, T.; Kishi, Y. Tetrahedron Lett.
1986, 27, 4763; (b) Piers, E.; Wong, T.; Coish, P. D.; Rogers, C. Can. J. Chem. 1994,
72, 1816; (c) Luo, F. T.; Hsieh, L. C. Tetrahedron Lett. 1994, 35, 9585.
10. (a) Wuts, P. G. M.; Greene, T. W. Greene’s Protective Groups in Organic Synthesis,
4th ed.; John Wiley: Hoboken, 2007; (b) Viterisi, A.; Orsini, A.; Weibel, J. M.;
Pale, P. Tetrahedron Lett. 2006, 47, 2779.
11. For one-step CeC bond formation reaction with desilylatoin, for example, see:
(a) Birkofer, L.; Uhlenbra.H; Ritter. Chem. Ber. 1963, 96, 3280; (b) Bourgeoi, P.;
Merault, G.; Calas, R. J. Organomet. Chem. 1973, 59, C4; (c) Lermontov, S. A.;
Rakov, I. M.; Zefirov, N. S.; Stang, P. J. Tetrahedron Lett. 1996, 37, 4051; (d) Ito, H.;
Arimoto, K.; Sensui, H.; Hosomi, A. Tetrahedron Lett. 1997, 38, 3977; (e) Hir-
abayashi, E.; Mori, A.; Kawashima, J.; Suguro, M.; Nishihara, Y.; Hiyama, T. J. Org.
Chem. 2000, 65, 5342; (f) Kang, S.-K.; Ryu, H.-C.; Hong, Y.-T. J. Chem. Soc., Perkin
Trans. 1 2001, 736; (g) Kabalka, G. W.; Wang, L.; Pagni, R. M. Tetrahedron 2001,
57, 8017; (h) Yang, C. L.; Nolan, S. P. Organometallics 2002, 21, 1020; (i) Halbes,
U.; Pale, P. Tetrahedron Lett. 2002, 43, 2039; (j) Sommer, W. J.; Weck, M. Adv.
Synth. Catal. 2006, 348, 2101; (k) Nishihara, Y.; Inoue, E.; Ogawa, D.; Okada, Y.;
Noyori, S.; Takagi, K. Tetrahedron Lett. 2009, 50, 4643; (l) Nishihara, Y.; Noyori,
S.; Okamoto, T.; Suetsugu, M.; Iwasaki, M. Chem. Lett. 2011, 40, 972.
12. Until more recently, the direct synthetic method of internal iodoalkenes from
silyl-substituted alkyne has not reported, see Sato, H. A.; Mihara, S.; Iwasawa, T.
Tetrahedron Lett. 2012, 53, 3585. Independently, we reported the desilylative
hydroiodination of silylalkynes in the 38th Symposium on main group element
chemistry in Kanazawa on 8th December 2011 (P-05).
13. Gomelya, N. D.; Feshchenko, N. G. Zh. Obshch. Khim. 1988, 58, 2652.
14. Gomelya, N. D.; Matyusha, A. G.; Feshchenko, N. G. Zh. Obshch. Khim. 1984, 54,
1242.
15. Gomelya, N. D.; Feshchenko, N. G. Zh. Obshch. Khim. 1987, 57, 1702.
16. Although the direct hydroiodination of 1-decyne with HI (53% aq) did not
proceed at all, in the precence of Ph2P(O)H hydroiodination of 1-decyne with HI
(53% aq) slightly proceeded (10% yield). So we consider Ph2P(O)H would acti-
vate hydroiodination via the formation of the complex Ph2P(O)H$HI.
17. Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley-Interscience: New
York, NY, 2000.
4. 3.12. 1-(1-Iodoethenyl)-4-(trifluoromethyl)benzene
(3l).31 Colorless oil; 1H NMR (400 MHz, CDCl3)
d
6.18 (d, J¼2.0 Hz,
1H), 6.54 (d, J¼2.0 Hz, 1H), 7.54e7.64 (m, 4H); 13C NMR (100 MHz,
CDCl3)
d
105.0, 125.3 (q, JCeF¼3.8 Hz), 126.8 (q, JCeF¼271.9 Hz),
128.5, 129.3, 130.2 (q, JCeF¼149.8 Hz), 145.2; MS (EI), m/z (%)¼298
(Mþ, 6), 171 (MþꢁI, 100).
4.3.13. 1-Cyano-4-(1-iodoethenyl)benzene (3m). Yellow paste; 1H
NMR (400 MHz, CDCl3)
d
6.21 (d, J¼1.8 Hz, 1H), 6.56 (d, J¼2.3 Hz,
1H), 7.44 (d, J¼8.2 Hz, 2H), 7.66 (d, J¼9.1 Hz, 2H); 13C NMR
(100 MHz, CDCl3)
d 112.7, 118.3, 128.7, 129.3, 132.1, 132.4, 147.5;
HRMS (EI) calcd for C9H6NI: 254.9545, found: 254.9540.
4.3.14. (Z)-3-Iodo-1-phenylnon-2-en-1-one (3n).9c Yellow oil; 1H
NMR (400 MHz, CDCl3)
d
0.87 (t, 3H, J¼6.4 Hz), 1.25e1.40 (m, 6H),
1.60e1.68 (m, 2H), 3.05 (t, 2H, J¼7.3 Hz), 7.44e7.48 (m, 2H),
7.54e7.60 (m, 1H), 7.62 (s, 1H), 7.91 (d, 2H, J¼8.2 Hz); 13C NMR
(100 MHz, CDCl3)
d 14.1, 22.6, 28.3, 29.9, 31.6, 42.1, 128.5, 128.7,
130.5, 133.2, 136.5, 137.9, 188.5; MS (EI), m/z (%)¼342 (Mþ, 1), 215
(MþꢁI, 100).
4.4. General procedure for the synthesis of internal io-
doalkenes from silylalkyne using iodine, Ph2P(O)H, and
Ph2P(O)OH
Under
a nitrogen atmosphere, diphenylphosphine oxide
(66.7 mg, 0.33 mmol) and diphenylphosphinic acid (70.4 mg,
0.33 mmol) were placed in a Schlenk tube at room temperature,
followed by CHCl3 (0.6 mL), iodine (58.4 mg, 0.23 mmol), and
alkyne (0.3 mmol). The mixture was stood statically for 16 h at
room temperature, and then MeOH (5 ml) was added to quench the
reaction. After a while, the crude solution turned colorless from
pale purple and white solid of Ph2P(O)OH was precipitated. The
precipitate was filtered, and the crude solution was purified by
preparative TLC (silica gel).
Acknowledgements
18. A main byproduct is 2-iodo-2-octene (cis/trans mixture) when 1-octyne was
used in higher temperature.
19. Nilssom, J.; Kraszewski, A.; Stawinski, J. J. Chem. Soc., Perkin Trans. 1 2001,
2, 2263.
20. When hydroiodination of 1-decyne with HI (53% aq) in CHCl3 was examined in
the presence of (PhO)2P(O)H, hydroiodination product was partly obtained
(34% yield).
21. It has been believed that hydrobromination of aliphatic internal alkynes pro-
ceeds by a concerted process by the reaction of alkyne with proton and bro-
mide anion. See Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, Part A,
5th ed.; Springer: New York, NY, USA, 2007, pp 539. In our hydroiodination,
anti-adducts are preferentially obtained. Therefore, we assume that the hy-
droiodination proceeds via the same process.
This work is supported by Grant-in-Aid for Scientific Research
(C, 23550057), from the Ministry of Education, Culture, Sports,
Science and Technology, Japan and by Industry-University Co-
operation Program of Sakai City. S-i.K. thanks Japan Society for the
Promotion of Science for its support of this work by Grant-in-Aid
for JSPS Fellows (No, 21-10516).
References and notes
1. Iodoalkenes were widely used as intermediates for organic synthesis. For ex-
amples, see: (a) Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W. Comprehensive
Organic Functional Group Transformations; Pergamon: Oxford, UK, 1995; Vol. 1;
22. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467; (b)
ꢀ
Chinchilla, R.; Najera, C. Chem. Rev. 2007, 107, 874.