H
N. Komami et al.
Paper
Synthesis
HRMS (ESI): m/z (M + Na+) calcd for C21H3070GeONa: 391.1431; found:
391.1431.
(7) (a) Spivey, A. C.; Gripton, C. J.; Noban, C.; Parr, N. J. Synlett 2005,
2167. (b) Zhang, Q.; Liu, C.; Shi, J.; Xu, Q.; Jin, L.; Zhao, C.; Zhang,
T. Synlett 2016, 27, 1945. (c) Ozaki, K.; Matsuoka, W.; Ito, H.;
Itami, K. Org. Lett. 2017, 19, 1930. (d) Ozaki, K.; Murai, K.;
Matsuoka, W.; Kawasumi, K.; Ito, H.; Itami, K. Angew. Chem. Int.
Ed. 2017, 56, 1361.
(8) Cross-coupling reactions of arylgermane derivatives: (a) Kosugi,
M.; Tanji, T.; Tanaka, Y.; Yoshida, A.; Fugami, K.; Kameyama, M.;
Migita, T. J. Organomet. Chem. 1996, 508, 255. (b) Faller, J. W.;
Kultyshev, R. G. Organometallics 2002, 21, 5911. (c) Nakamura,
T.; Kinoshita, H.; Shinokubo, H.; Oshima, K. Org. Lett. 2002, 4,
3165. (d) Enokido, T.; Fugami, K.; Endo, M.; Kameyama, M.;
Kosugi, M. Adv. Synth. Catal. 2004, 346, 1685. (e) Endo, M.;
Fugami, K.; Enokido, T.; Sano, H.; Kosugi, M. Adv. Synth. Catal.
2007, 349, 1025. (f) Spivey, A. C.; Tseng, C.-C.; Hannah, J. P.;
Gripton, C. J. G.; de Fraine, P.; Parr, N. J.; Scicinski, J. J. Chem.
Commun. 2007, 2926. (g) Pitteloud, J.-P.; Zhang, Z.-T.; Liang, Y.;
Cabrera, L.; Wnuk, S. F. J. Org. Chem. 2010, 75, 8199. (h) Zhang,
Z.-T.; Pitteloud, J.-P.; Cabrera, L.; Liang, Y.; Toribio, M.; Wnuk, S.
F. Org. Lett. 2010, 12, 816.
Methyl (S)-2-[(tert-Butoxycarbonyl)amino]-3-[4-(trimethyl-
germyl)phenyl]propanoate (4u)
Conditions B using methyl (S)-2-[(tert-butoxycarbonyl)amino]-3-(4-
{[(trifluoromethyl)sulfonyl]oxy}phenyl)propanoate (2u) and KOAc in-
stead of Cs2CO3 for 62 h, and purification of the crude product by sili-
ca gel column chromatography (hexane/EtOAc 10:1) afforded 4u as a
colorless solid (132.6 mg, 67%); mp 55.5–56.2 °C; Rf = 0.50 (EtOAc/
MeOH 9:1).
IR (KBr): 3370, 2975, 1747, 1717, 1500, 1437, 1366, 1248, 1214, 1168,
825, 757, 600, 568 cm–1
.
1H NMR (500 MHz, CDCl3,50 °C): δ = 7.39 (d, J = 8.0 Hz, 2 H), 7.10 (d,
J = 8.0 Hz, 2 H), 4.96–4.87 (m, 1 H), 4.62–4.52 (m, 1 H), 3.71 (s, 3 H),
3.13–3.06 (m, 1 H), 3.05–2.93 (m, 1 H), 1.40 (s, 9 H), 0.36 (s, 9 H).
13C NMR (125 MHz, CDCl3): δ = 172.3, 155.0, 140.9, 135.9, 133.1,
128.9, 79.8, 54.3, 52.2, 38.2, 28.3, –1.85.
HRMS (ESI): m/z (M + Na+) calcd for C18H2970GeNO4Na: 416.1231;
(9) (a) Matsumoto, H.; Nagashima, S.; Yoshihiro, K.; Nagai, Y.
J. Organomet. Chem. 1975, 85, C1. (b) Azarian, D.; Dua, S. S.;
Eaborn, C.; Walton, D. R. M. J. Organomet. Chem. 1976, 117, C55.
(c) Matsumoto, H.; Yoshihiro, K.; Nagashima, S.; Watanabe, H.;
Nagai, Y. J. Organomet. Chem. 1977, 128, 409. (d) Eaborn, C.;
Griffiths, R. W.; Pidcock, A. J. Organomet. Chem. 1982, 225, 331.
(e) Hatanaka, Y.; Hiyama, T. Tetrahedron Lett. 1987, 28, 4715.
(f) Gooßen, L. J.; Ferwanah, A.-R. S. Synlett 2000, 1801.
(g) Shirakawa, E.; Kurahashi, T.; Yoshida, H.; Hiyama, T. Chem.
Commun. 2000, 1895. (h) Denmark, S. E.; Kallemeyn, J. M. Org.
Lett. 2003, 5, 3483. (i) Iwasawa, T.; Komano, T.; Tajima, A.;
Tokunaga, M.; Obora, Y.; Fujihara, T.; Tsuji, Y. Organometallics
2006, 25, 4665. (j) McNeill, E.; Barder, T. E.; Buchwald, S. L. Org.
Lett. 2007, 9, 3785.
found: 416.1234.
Funding Information
This work was supported in part by JSPS KAKENHI Grant Number
JP15H05802 in Precisely Designed Catalysts with Customized Scaf-
folding.
)(
Supporting Information
Supporting information for this article is available online at
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
ortioInfgrmoaitn
(10) (a) Murata, M.; Suzuki, K.; Watanabe, S.; Masuda, Y. J. Org.
Chem. 1997, 62, 8569. (b) Manoso, A. S.; DeShong, P. J. Org.
Chem. 2001, 66, 7449. (c) Murata, M.; Ishikura, M.; Nagata, M.;
Watanabe, S.; Masuda, Y. Org. Lett. 2002, 4, 1843. (d) Yamanoi,
Y. J. Org. Chem. 2005, 70, 9607. (e) Hamze, A.; Provot, O.; Alami,
M.; Brion, J.-D. Org. Lett. 2006, 8, 931. (f) Yamanoi, Y.; Nishihara,
H. Tetrahedron Lett. 2006, 47, 7157. (g) Murata, M.; Yamasaki,
H.; Ueta, T.; Nagata, M.; Ishikura, M.; Watanabe, S.; Masuda, Y.
Tetrahedron 2007, 63, 4087. (h) Murata, M.; Yamasaki, H.;
Uogishi, K.; Watanabe, S.; Masuda, Y. Synthesis 2007, 2944.
(i) Yamanoi, Y.; Taira, T.; Sato, J.-i.; Nakamula, I.; Nishihara, H.
Org. Lett. 2007, 9, 4543. (j) Yamanoi, Y.; Nishihara, H. J. Org.
Chem. 2008, 73, 6671. (k) Lesbani, A.; Kondo, H.; Yabusaki, Y.;
Nakai, M.; Yamanoi, Y.; Nishihara, H. Chem. Eur. J. 2010, 16,
13519. (l) Yamanoi, Y.; Sendo, J.; Kobayashi, T.; Maeda, H.;
Yabusaki, Y.; Miyachi, M.; Sakamoto, R.; Nishihara, H. J. Am.
Chem. Soc. 2012, 134, 20433. (m) Chen, L.; Huang, J.-B.; Xu, Z.;
Zheng, Z.-J.; Yang, K.-F.; Cui, Y.-M.; Cao, J.; Xu, L.-W. RSC Adv.
2016, 6, 67113. (n) Xu, Z.; Xu, J.-Z.; Zhang, J.; Zheng, Z.-J.; Cao, J.;
Cui, Y.-M.; Xu, L.-W. Chem. Asian J. 2017, 12, 1749.
References
(1) (a) Denmark, S. E.; Sweis, R. F. In Metal-Catalyzed Cross-Coupling
Reactions; de Meijere, A.; Diederich, F., Eds.; Wiley-VCH: Wein-
heim, 2008, 163. (b) Chan, T. H.; Fleming, I. Synthesis 1979, 761.
(c) Hosomi, A.; Miura, K. Bull. Chem. Soc. Jpn. 2004, 77, 835.
(d) Denmark, S. E.; Ambrosi, A. Org. Process Res. Dev. 2015, 19,
982. (e) Komiyama, T.; Minami, Y.; Hiyama, T. ACS Catal. 2017,
7, 631.
(2) (a) Mitchell, T. N. In Metal-Catalyzed Cross-Coupling Reactions;
de Meijere, A.; Diederich, F., Eds.; Wiley-VCH: Weinheim, 2008,
125. (b) Ingham, R. K.; Rosenberg, S. D.; Gilman, H. Chem. Rev.
1960, 60, 459.
(3) (a) Akiyama, T. In Main Group Metals in Organic Synthesis;
Yamamoto, H.; Oshima, K., Eds.; Wiley-VCH: Weinheim, 2004,
593–620. (b) Quane, D.; Bottei, R. S. Chem. Rev. 1963, 63, 403;
and references cited therein.
(4) (a) Eaborn, C.; Pande, K. C. J. Chem. Soc. 1960, 1566.
(b) Moerlein, S. M. J. Chem. Soc., Perkin Trans. 1 1985, 1687.
(c) Coenen, H. H.; Moerlein, S. M. J. Fluorine Chem. 1987, 36, 63.
(d) Moerlein, S. M. J. Org. Chem. 1987, 52, 664.
(11) Reddy, P. N.; Hayashi, T.; Tanaka, M. Chem. Lett. 1991, 20, 677.
(12) Goodson, F. E.; Wallow, T. I.; Novak, B. M. J. Am. Chem. Soc. 1997,
119, 12441; and references cited therein.
(13) Grundy, S. M.; Ahrens, E. H. Jr.; Salen, G.; Schreibman, P. H.;
Nestel, P. J. J. Lipid Res. 1972, 13, 531.
(14) Yang, J.; Teng, Y.; Ara, S.; Rallapalli, S.; Cook, J. M. Synthesis 2009,
1036.
(5) (a) Dallaire, C.; Brook, M. A. Organometallics 1990, 9, 2873.
(b) Dallaire, C.; Brook, M. A. Organometallics 1993, 12, 2332.
(6) (a) Boyer, I. J. Toxicology 1989, 55, 253. (b) Arylgermanes are
generally less toxic even compared with organosilanes:
Lukevics, E.; Ignatovich, L. Appl. Organometal. Chem. 1992, 6,
113.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I