Total Synthesis of Spiro[cyclohexane-2-indoline] Alkaloids: A Regio- and Diastereoselective Spirocyclization Approach.
Indolines
Kopsia Alkaloids
Spiro Compounds
Spirocyclization
Total Synthesis
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
05 12 2022
05 12 2022
Historique:
received:
15
08
2022
pubmed:
13
10
2022
medline:
1
12
2022
entrez:
12
10
2022
Statut:
ppublish
Résumé
A direct spirocyclization approach for the chemical synthesis of spiro[cyclohexane-2-indoline] alkaloids is reported. The absolute stereochemistry was introduced by a desymmetrizing Dieckmann condensation, and the relative stereochemistry was controlled by the manipulation of the kinetic and thermodynamic pathways of the spirocyclization. By contrast to the biogenetic proposal involving the diester-type alkaloid as the precursor, we demonstrate that chemically a common lactone-type intermediate could bridge the chemical synthesis of this class of natural products.
Identifiants
pubmed: 36224105
doi: 10.1002/anie.202212042
doi:
Substances chimiques
indoline
6DPT9AB2NK
Alkaloids
0
Indoles
0
Cyclohexanes
0
Spiro Compounds
0
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202212042Informations de copyright
© 2022 Wiley-VCH GmbH.
Références
K. Awang, T. Sevenet, A. Hamid, A. Hadi, B. David, M. Pais, Tetrahedron Lett. 1992, 33, 2493-2496;
K. Awang, T. Sevenet, M. Pais, A. Hamid, A. Hadi, J. Nat. Prod. 1993, 56, 1134-1139;
T.-S. Kam, K.-H. Lim, K. Yoganathan, M. Hayashi, K. Komiyama, Tetrahedron 2004, 60, 10739-10745;
W.-S. Yap, C.-Y. Gan, Y.-Y. Low, Y.-M. Choo, T. Etoh, M. Hayashi, K. Komiyama, T.-S. Kam, J. Nat. Prod. 2011, 74, 1309-1312;
S. Arai, M. Nakajima, A. Nishida, Alkaloids Chem. Biol. Perspect. 2017, 78, 167-204;
M. S. Kirillova, F. M. Miloserdov, A. M. Echavarren, Org. Chem. Front. 2018, 5, 273-287.
For a recent review on the synthesis of kopsinine-type natural products: B. Qin, Y. Wang, X. Wang, Y. Jia, Org. Chem. Front. 2021, 8, 369-383.
For the total synthesis of the lactone-type alkaloids, see:
W. H. Pearson, Y. Mi, Y. Lee III, P. Stoy, J. Am. Chem. Soc. 2001, 123, 6724-6725;
W. H. Pearson, Y. Mi, Y. Lee III, P. Stoy, J. Org. Chem. 2004, 69, 9109-9122;
M. Nakajima, S. Arai, A. Nishida, Angew. Chem. Int. Ed. 2016, 55, 3473-3476;
Angew. Chem. 2016, 128, 3534-3537;
Y. Gao, M. Fan, Q. Geng, D. Ma, Chem. Eur. J. 2018, 24, 6547-6550.
For the total synthesis of the cyclopropane-type alkaloids, see:
M. Hoshi, O. Kaneko, M. Nakajima, S. Arai, A. Nishida, Org. Lett. 2014, 16, 768-771;
S. Arai, M. Nakajima, A. Nishida, Angew. Chem. Int. Ed. 2014, 53, 5569-5572;
Angew. Chem. 2014, 126, 5675-5678;
M. Nakajima, S. Arai, A. Nishida, Chem. Asian J. 2015, 10, 1065-1070;
S. Jin, J. Gong, Y. Qin, Angew. Chem. Int. Ed. 2015, 54, 2228-2231;
Angew. Chem. 2015, 127, 2256-2259;
H. Huang, S. Jin, J. Gong, D. Zhang, H. Song, Y. Qin, Chem. Eur. J. 2015, 21, 13284-13290;
M. S. Kirillova, M. E. Muratore, R. Dorel, A. M. Echavarren, J. Am. Chem. Soc. 2016, 138, 3671-3674;
W. Xu, J. Zhao, C. Tao, H. Wang, Y. Li, B. Cheng, H. Zhai, Org. Lett. 2018, 20, 1509-1512;
A. Nash, X. Qi, P. Maity, K. Owens, U. K. Tambar, Angew. Chem. Int. Ed. 2018, 57, 6888-6891;
Angew. Chem. 2018, 130, 7004-7007.
C. Wang, Z. Wang, X. Xie, X. Yao, G. Li, L. Zu, Org. Lett. 2017, 19, 1828-1830.
F. M. Miloserdov, M. S. Kirillova, M. E. Muratore, A. M. Echavarren, J. Am. Chem. Soc. 2018, 140, 5393-5400.
For examples of 5-exo addition:
K. Muñiz, A. Lishchynskyi, J. Streuff, M. Nieger, E. C. Escudero-Adan, M. M. Belmonte, Chem. Commun. 2011, 47, 4911-4913;
R. Miyaji, K. Asano, S. Matsubara, Org. Lett. 2013, 15, 3658-3661;
K. T. Tarantino, D. C. Miller, T. A. Callon, R. R. Knowles, J. Am. Chem. Soc. 2015, 137, 6440-6443.
For examples of 6-endo addition:
M. Castaing, S. L. Wason, B. Estepa, J. F. Hooper, M. C. Willis, Angew. Chem. Int. Ed. 2013, 52, 13280-13283;
Angew. Chem. 2013, 125, 13522-13525;
S. Cheng, L. Zhao, S. Yu, Adv. Synth. Catal. 2014, 356, 982-986;
K. Saito, Y. Moriya, T. Akiyama, Org. Lett. 2015, 17, 3202-3205.
R. Sengupta, J. A. Witek, S. M. Weinreb, Tetrahedron 2011, 67, 8229-8234.
T. Kan, T. Fujimoto, S. Ieda, Y. Asoh, H. Kitaoka, T. Fukuyama, Org. Lett. 2004, 6, 2729-2731.
X. Zeng, Z. Cao, Y. Wang, F. Zhou, J. Zhou, Chem. Rev. 2016, 116, 7330-7396.
Y. Nagao, Y. Hagiwara, T. Tohjo, Y. Hasegawa, M. Ochiai, M. Shiro, J. Org. Chem. 1988, 53, 5983-5986.
Using L-menthol as the directing group failed to produce 15.
Deposition number 2201434 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.
Y. Li, Q. Shao, H. He, C. Zhu, X.-S. Xue, J. Xie, Nat. Commun. 2022, 13, 10.
Deposition number 2201436 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.
Deposition number 2201437 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.
E. E. Schultz, B. G. Pujanauski, R. Sarpong, Org. Lett. 2012, 14, 648-651.