Chemistry - A European Journal
10.1002/chem.201800829
FULL PAPER
Conclusions
4212; b) M. Marigo, T. C. Wabnitz, D. Fielenbach, K. A. Jørgensen,
Angew. Chem. 2005, 117, 804; Angew. Chem. Int. Ed. 2005, 44, 794.
6] Y. Hayashi, S. Umemiya, Angew. Chem. 2013, 125, 3534; Angew. Chem.
Int. Ed. 2013, 52, 3450.
[
[
[
In summary, a diastereo- and enantioselective total synthesis of
Latanoprost (1) has been accomplished. The present route
possesses several noteworthy features; 1) one of the key
reactions is the organocatalyst-mediated 3+2 cycloaddition
reaction developed by our group for the construction of the
cyclopentane core structure. 2) Chirality in the w-side chain is
generated by the catalytic asymmetric a-aminoxylation by
potassium prolinate also developed by our group. 3) In the
addition reaction of the alkynyl group, complete epimerization
from cis to trans occurred before the alkynyl addition. 4)
Excellent 1,3-chiral induction was realized in the domino
7] S. Umemiya, D. Sakamoto, G. Kawauchi, Y. Hayashi, Org. Lett. 2017, 19,
1112.
8] a) Y. Hayashi, T. Saitoh, H. Arase, G. Kawauchi, N. Takeda, Y. Shimasaki, I.
Sato, Chem. Eur. J. DOI: 10.1002/chem.201705930; b) P. A. Ev ans , A.
Grisin, M. J. Lawler, J. Am. Chem. Soc. 2012, 134, 2856.
[9] a) Y. Hayashi, N. Umekubo, T. Hirama, Org. Lett. 2017, 19, 4155; b) Y.
Hayashi, J. Yamaguchi, K. Hibino, M. Shoji, Tetrahedron Lett. 2003, 44,
8293; c) Y. Hayashi, J. Yamaguchi, T. Sumiya, M. Shoji, Angew. Chem.
2004, 116, 1132; Angew. Chem. Int. Ed. 2004, 43, 1112; d) Y. Hayashi,
J. Yamaguchi, T. Sumiya, K. Hibino, M. Shoji, J. Org. Chem. 2004, 69,
966; e) S. P. Brown, M. P. Brochu, C. J. Sinz, D. W. C. MacMillan, J.
5
acetalization and oxy-Michael reaction catalyzed by Bi(OTf)
NaClO which was developed in our group. 5) Highly
diastereoselective reduction of the ketone at C11 by the
3
and
Am. Chem. Soc. 2003, 125, 10808; f) G. Zhong, Angew. Chem. 2003,
115, 4379; Angew. Chem. Int. Ed. 2003, 42, 4247; g) A. Bøgevig, H.
Sundén, A. Córdova, Angew. Chem. 2004, 116, 112; Angew. Chem. Int.
Ed. 2004, 43, 1109.
4
,
4 4
combination of NaBH and Ti(OiPr) proceeded without affecting
[
[
[
[
10] W. S. Wadsworth, W. D. Emmons J. Am. Chem. Soc. 1961, 83, 1733.
11] N. Momiyama, H. Yamamoto, J. Am. Chem. Soc. 2003, 125, 6038.
12] Y. Hayashi, Chem. Sci. 2016, 7, 866.
the ester moiety.
13] a) M. J. Gaunt, J. Yu, J. B. Spencer, J. Org. Chem. 1998, 63, 4172; b) J.
Xia, S. A. Abbas, R. D. Locke, C. F. Piskorz, J. L. Alderfer, K. L. Matta,
Tetrahedron Lett. 2000, 41, 169.
Acknowledgements
[
[
[
14] a) T. Satoh, K. Nanba, S. Suzuki, Chem. Pharm. Bull. 1971, 19, 817; b) Y.
Suga, H. Fuwa, M. Sasaki, J. Org. Chem. 2014, 79, 1656.
15] D. E. Frantz, R. Fässler, E. M. Carreira, J. Am. Chem. Soc. 2000, 122,
This work was supported by JSPS KAKENHI Grant Number
JP16H01128 in Middle Molecular Strategy.
1806.
Keywords: Organocatalyst • Total synthesis • Latanoprost •
16] R. Ballini, R. Castagnani, M. Petrini, J. Org. Chem. 1992, 57, 2160.
Asymmetric synthesis • One pot reaction
[17] a) S. Umemiya, K. Nishino, I. Sato, Y. Hayashi, Chem. Eur. J. 2014, 20,
5753. Reviews of Nef reaction, see; b) R. Ballini, M. Petrini,
Tetrahedron 2004, 60, 1017; c) R. Ballini, M. Petrini, Adv. Synth. Catal.
015, 357, 2371.
1
[1] B. Resul, J. Stjernschantz, K. No, C. Liljebris, G. Selen, M. Astin, M.
Karlsson, L. Z. Bito J. Med. Chem. 1993, 36, 243.
2
[
18] a) P. J. Stephen, F. J. Devlin, J. -J. Pan, Chirality 2008, 20, 643; b) Y. He,
B. Wong, R. K. Dukor, Appl. Spectrosc. 2011, 65, 699; c) T. Taniguchi,
K. Nakano, R. Baba, K. Monde, Org. Lett. 2017, 19, 404; d) For the
application of VCD in the organocatalytic reaction, see; M. G. Capdevila,
F. Benfatti, L. Zoli, M. Stenta, P. G. Cozzi, Chem. Eur. J. 2010, 16,
[
2] a) B. Resul, J. Stjernschantz, K. No, C. Liljebris, G. Selen, M. Astin, M.
Karlsson, L. Z. Bito, J. Med. Chem. 1993, 36, 243; b) I. Obadalová, T.
Pilarčík, M. Slavíková, J. Hájíček, Chirality, 2005, 17, 109; c) J. G.
Martynow, J. Jóźwik, W. Szelejewski, O. Achmatowicz, A. Kutner, K.
Wiśniewski, J. Winiarski, O. Zegrocka-Stendel, P. Gołębiewski, Eur. J.
Org. Chem. 2007, 689; d) G. Zanoni, A. D’Alfonso, A. Porta, L. Feliciani,
S. P. No lan, G. Vidari, Tetrahedron 2010, 66, 7472; e) K Vijendhar, B
Srinivas, S. Boodida, J. Chem. Sci. 2015, 127, 2023. Formal total
syntheses; f) M. Harikrishna, H. R. Mohan, P. K. Dubey, M. Shankar, G.
V. Subbaraju, Asian. J. Chem. 2011, 23, 3121; g) M. L. Contente, P.
Zambelli, S. Galafassi, L. Tamborini, A. Pinto, P. Conti, F. Modinari, D.
Romano, J. Mol. Catal. B: Enzym. 2015, 114, 7.
1
1237.
19] NaBH /Ti(OPr)
801. LiBH
i
[
4
4
: C. Bonini, G. Righi, L. Rossi. Tetrahedron 1992, 48,
i
9
4
/Ti(OPr)
4
: A. Matsumoto, K. Asano, S. Matsubara, Synlett
i
2015, 26, 1872.
NaBH
4
/Ti(OPr)
4
(reductive amination)
:
a) S.
Bhattacharyya, O. W. Gooding, J. Labadie, Tetrahedron Lett. 2003, 44,
6099; b) M. Dalai, M. Periasamy, Tetrahedron Asymmetry 2009, 20,
1247.
[
20] H. Ohmiya, M. Yang, Y. Yamauchi, Y. Ohtsuka, M. Sawamura, Org. Lett.
010, 12, 1796.
[
3] S. Prévost, K. Thai, N. Schützenmeister, G. Coulthard, W. Erb, V. K.
2
Aggarwal, Org. Lett. 2015, 17, 504.
[21] S. Chandrasekhar, B. Saritha, V. Jagadeshwar, S. J. Prakash,
[4] S. Umemiya, Y. Hayashi, Eur. J. Org. Chem. 2015, 4320.
Tetrahedron Asymmetry 2006, 17, 1380.
[5] Diphenylprolinol silyl ether see; a) Y. Hayashi, H. Gotoh, T. Hayashi, M.
Shoji, Angew. Chem. 2005, 117, 4284; Angew. Chem. Int. Ed. 2005, 44,
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