Bioinspired Total Syntheses of Secologanin-Related Natural Products: A Demonstration of the Power of Secologanin in the Flask

Abstract

The preparation of natural product libraries by total synthesis has become an extremely important and attractive research topic in organic chemistry. In higher plants, secologanin, which belongs to the monoterpene family, is the starting point for derivation into natural products with different skeletons and biological activities. This Account presents a practical total synthesis of secologanin using an asymmetric organocatalytic cascade reaction. In addition, a collective total synthesis of secologanin-related natural products, such as monoterpenoid indole alkaloids and hetero-oligomeric iridoid glycosides, is described from the synthesized secologanin and its derivatives. To date, we have successfully synthesized 39 secologanin-related natural products using bioinspired strategies with reference to biosynthesis, and in this Account, details of the synthetic strategies for 20 of them are presented. By combining these total syntheses into a single Account, we hope to provide a better view of how the pieces connect to one another and how each piece fits together into the overall body of work.

1 Introduction

2 A Practical Total Synthesis of Secologanin

3 Total Syntheses of 5-Carboxystrictosidine and Related Indole Alkaloid Glycosides

4 Total Syntheses of Strictosidine and Related Indole Alkaloid Glycosides

5 Total Syntheses of β-Carboline-Type Monoterpenoid Indole Alkaloid Glycosides

6 Total Syntheses of Non-Glycosylated Monoterpenoid Indole Alkaloids

7 Total Syntheses of Hetero-Oligomeric Iridoid Glycosides

8 Conclusion and Future Prospects

Key words

secologanin - bioinspired transformation - monoterpenoid indole alkaloid - hetero-oligomeric iridoid glycoside - collective total synthesis

Publication History

Received: 07 April 2023

Accepted after revision: 24 April 2023

Accepted Manuscript online:
24 April 2023

Article published online:
25 May 2023

• References

• 1a Newman DJ, Cragg GM. J. Nat. Prod. 2020; 83: 770
• 1b Atanasov AG, Zotchev SB, Dirsch VM, ; The International Natural Product Sciences Taskforce; Supuran CT. Nat. Rev. Drug Discovery 2021; 20: 200
• 2 Baran PS. J. Am. Chem. Soc. 2018; 140: 4751

For reviews on the biomimetic synthesis of indole alkaloids, see:
• 3a Michel S, Tillequin F. Biomimetic Organic Synthesis . Poupon E, Nay B. Wiley-VCH; Weinheim: 2011: 91-116
• 3b Takayama H, Sakai S. The Alkaloids, Vol. 50. Cordell GA. Academic Press; New York: 1998: 415-452
• 4a Boros CA, Stermitz ER. J. Nat. Prod. 1990; 53: 1055
• 4b Boros CA, Stermitz ER. J. Nat. Prod. 1991; 54: 1173
• 4c Murata J, Roepke J, Gordon H, Luca VD. Plant Cell 2008; 20: 524
• 5a Cordell GA. In Introduction to Alkaloids: A Biogenetic Approach . Wiley-Interscience; New York: 1981
• 5b Pelletier SW. In The Alkaloids: Chemical and Biological Perspectives, Vol. 1. Pelletier SW. Wiley; New York: 1983
• 5c Indoles and Biogenetically Related Alkaloids . Phillipson JD, Zenk MH. Academic Press; London: 1980
• 5d Indoles, The Monoterpenoid Indole Alkaloids. In The Chemistry of Heterocyclic Compounds, Part 4, Vol. 25. Saxton JE. Wiley; New York: 1983
• 5e The Monoterpenoid Indole Alkaloids. In The Chemistry of Heterocyclic Compounds, Suppl., Part 4, Vol. 25. Saxton JE. Wiley; New York: 1994
• 5f Saxton JE. Nat. Prod. Rep. 1997; 14: 559
• 5g Leonard J. Nat. Prod. Rep. 1999; 16: 319
• 5h Cordell GA, Quinn-Beattie ML, Farnsworth NR. Phytother. Res. 2001; 15: 183
• 5i O’Connor SE, Maresh JJ. Nat. Prod. Rep. 2006; 23: 532
• 5j Pickens LB, Tang Y, Chooi Y.-H. Annu. Rev. Chem. Biomol. Eng. 2011; 2: 211
• 5k Amirkia V, Heinrich M. Phytochem. Lett. 2014; 10: xlviii
• 6a Kauno I, Tsuboi A, Nanri M, Kawano N. Phytochemistry 1990; 29: 338
• 6b Tomita H, Mouri Y. Phytochemistry 1996; 42: 239
• 6c Tian X.-Y, Wang Y.-H, Yu S.-S, Fang W.-S. Org. Lett. 2006; 8: 2179
• 6d Tian X.-Y, Wang Y.-H, Liu H.-Y, Yu S.-S, Fang W.-S. Chem. Pharm. Bull. 2007; 55: 1677
• 6e Gülcemal D, Masullo M, Alankuş-Çalışkan O, Karayıldırım T, Șenol SG, Piacente S, Bedir E. Magn. Reson. Chem. 2010; 48: 239
• 6f Li F, Tanaka K, Watanabe S, Tezuka Y, Saiki I. Chem. Pharm. Bull. 2013; 61: 1318
• 6g Sun X, Ma G, Zhang D, Huang W, Ding G, Hu H, Tu G, Guo B. Molecules 2015; 20: 2165
• 6h Li F, Tanaka K, Watanabe S, Tezuka Y. Nat. Prod. Commun. 2016; 11: 891
• 6i Duan X.-Y, Ai L.-Q, Qian C.-Z, Zhang M.-D, Mei R.-Q. Phytochem. Lett. 2019; 33: 17
• 6j Yu Z.-P, Wang Y.-Y, Yu S.-J, Bao J, Yu J.-H, Zhang H. Fitoterapia 2019; 135: 99
• 6k Li F, Nishidono Y, Tanaka K, Watanabe S, Tezuka Y. Nat. Prod. Commun. 2020; 15
• 7a Rakumitsu K, Sakamoto J, Ishikawa H. Chem. Eur. J. 2019; 25: 8996
• 7b Anthony SM, Tona V, Zou Y, Morrill LA, Billingsley JM, Lim M, Tang Y, Houk KN, Garg NK. J. Am. Chem. Soc. 2021; 143: 7471
• 8a Sakamoto J, Umeda Y, Rakumitsu K, Sumimoto M, Ishikawa H. Angew. Chem. Int. Ed. 2020; 59: 13414 ; Angew. Chem. 2020, 132, 13516
• 8b Sakamoto J, Ishikawa H. Chem. Eur. J. 2022; 28: e202104052
• 8c Nakashima N, Sakamoto J, Rakumitsu K, Kitajima M, Juliawaty LD, Ishikawa H. Chem. Pharm. Bull. 2022; 70: 187
• 8d Sakamoto J, Kitajima M, Ishikawa H. Chem. Pharm. Bull. 2022; 70: 662
• 8e Yoshidome A, Sakamoto J, Kohara M, Shiomi S, Hokaguchi M, Hitora Y, Kitajima M, Tsukamoto S, Ishikawa H. Org. Lett. 2023; 25: 347
• 8f Sakamoto J, Kitajima M, Ishikawa H. Chem. Eur. J. 2023; 29: e202300179
• 8g Sakamoto J, Hiruma D, Kitajima M, Ishikawa H. Synlett 2023; 34: in press
• 9a Fukuyama T, Lin SC, Li L. J. Am. Chem. Soc. 1990; 112: 7050
• 9b Tokuyama H, Yokoshima S, Yamashita T, Lin S.-C, Li L, Fukuyama T. Synthesis 2002; 1121
• 10a Mangion IK, MacMillan DW. C. J. Am. Chem. Soc. 2005; 127: 3696
• 10b Zhang W, Ding M, Li J, Guo Z, Lu M, Chen Y, Liu L, Shen Y.-H, Li A. J. Am. Chem. Soc. 2018; 140: 4227
• 11a De Silva KT. D, King D, Smith GN. J. Chem. Soc. D 1971; 908
• 11b Ferrari F, Messana I, Botta B. J. Nat. Prod. 1986; 49: 1150
• 11c Kitajima M, Hashimoto K, Yokoya M, Takayama H, Aimi N, Sakai S. Chem. Pharm. Bull. 2000; 48: 1410
• 11d Onozawa T, Kitajima M, Kogure N, Peerakam N, Santiarworn D, Takayama H. J. Nat. Prod. 2017; 80: 2156
• 12 Brown RT, Charalambides AA. J. Chem. Soc., Chem. Commun. 1973; 765
• 13a Neimann K, Neumann R. Org. Lett. 2000; 2: 2861
• 13b Kobayashi S, Tanaka H, Amii H, Uneyama K. Tetrahedron Lett. 2003; 59: 1547
• 13c Berkessel A, Adrio JA. J. Am. Chem. Soc. 2006; 128: 13412
• 13d Berkessel A, Andrio JA. Adv. Synth. Catal. 2004; 346: 275
• 13e Hernandez LW, Pospech J, Klöckner U, Bingham TW, Sarlah D. J. Am. Chem. Soc. 2017; 139: 15656
• 14a Smith GN. Chem. Commun. 1968; 912
• 14b Brown RT, Smith GN, Stapleford KS. J. Tetrahedron Lett. 1968; 9: 4349
• 14c De Silva KT. D, Smith GN, Warren KE. H. J. Chem. Soc. D 1971; 905
• 14d Stöckigt J, Zenk MH. J. Chem. Soc., Chem. Commun. 1977; 646
• 14e Patthy-Lukáts Á, Károlyházy L, Szabó LF, Podányi B. J. Nat. Prod. 1997; 60: 69
• 14f Patthy-Lukáts Á, Kocsis Á, Szabó LF, Podányi B. J. Nat. Prod. 1999; 62: 1492
• 15 Stöckigt J, Barleben L, Panjikar S, Loris EA. Plant Physiol. Biochem. 2008; 46: 340
• 16a Brown RT, Chapple CL, Lashford AG. Phytochemistry 1977; 16: 1619
• 16b Zeches M, Richard B, Gueye-M’Bahia L, Le Men-Olivier L, Delaude C. J. Nat. Prod. 1985; 48: 42
• 16c Morita H, Ichihara Y, Takeya K, Watanabe K, Itokawa H, Motidome M. Planta Med. 1989; 55: 288
• 16d Erdelmeier CA. J, Wright AD, Orjala J, Baumgartner B, Rali T, Sticher O. Planta Med. 1991; 57: 149
• 16e Zhang Z, ElSohly HN, Jacob MR, Pasco DS, Walker LA, Clark AM. J. Nat. Prod. 2001; 64: 1001
• 16f Kitajima M, Yoshida S, Yamagata K, Nakamura M, Takayama H, Saito K, Seki H, Aimi N. Tetrahedron 2002; 58: 9169
• 16g Kitajima M, Fujii N, Yoshino F, Sudo H, Saito K, Aimi N, Takayama H. Chem. Pharm. Bull. 2005; 53: 1355
• 16h Faria EO, Kato L, de Oliveira CM. A, Carvalho BG, Silva CC, Sales LS, Schuquel IT. A, Silveira-Lacerda EP, Delprete PG. Phytochem. Lett. 2010; 3: 113
• 16i Huang X, Li Y, Su Y, Chai X, Yan S. Phytochem. Lett. 2014; 7: 30
• 16j Zhang Z.-J, Du R.-N, He J, Wu X.-D, Li Y, Li R.-T, Zhao Q.-S. Helv. Chim. Acta 2016; 99: 157
• 16k Jiang H, Liu Y.-B, Li Y, Li L, Ma S.-G, Qu J, Yu S.-S. Tetrahedron 2016; 72: 1276
• 16l Berger A, Tanuhadi E, Brecker L, Schinnerl J, Valant-Vetschera K. Phytochemistry 2017; 143: 124
• 16m Yüce I, Agnaniet H, Morlock GE. ACS Omega 2019; 4: 5038
• 17a Mesia K, Cimanga RK, Dhooghe L, Cos P, Apers S, Totté J, Tona GL, Pieters L, Vlietinck AJ, Maes L. J. Ethnopharmacol. 2010; 131: 10
• 17b Li Z, Li Z, Lin Y, Meng Z, Ding G, Cao L, Li N, Liu W, Xiao W, Wu X, Xu J. Chem. Biol. Drug Des. 2015; 86: 523
• 17c Kuete V, Sandjo LP, Mbaveng AT, Seukep JA, Ngadjui BT, Efferth T. BMC Complementary Altern. Med. 2015; 15: 309
• 17d Liew SY, Khaw KY, Murugaiyah V, Looi CY, Wong YL, Mustafa MR, Litaudon M, Awang K. Phytomedicine 2015; 22: 45
• 17e Li D, Chen J, Ye J, Zhai X, Song J, Jiang C, Wang J, Zhang H, Jia X, Zhu F. J. Ethnopharmacol. 2017; 196: 66
• 18 Lémus C, Kritsanida M, Canet A, Genta-Jouve G, Michel S, Deguin B, Grougnet R. Tetrahedron Lett. 2015; 56: 5377
• 19a Dou Y, Kouklovsky C, Gandon V, Vincent G. Angew. Chem. Int. Ed. 2020; 59: 1527 ; Angew. Chem. 2020, 132, 1543
• 19b Dou Y, Kouklovsky C, Vincent G. Chem. Eur. J. 2020; 26: 17190
• 20a Levesque J, Pousset JL, Cave A. C. R. Seances Acad. Sci., Ser C 1975; 280: 593
• 20b Aimi N, Murakami H, Tsuyuki T, Nishiyama T, Sakai S, Haginiwa J. Chem. Pharm. Bull. 1986; 34: 3064
• 21 Aimi N, Tsuyuki T, Murakami H, Sakai S, Haginiwa J. Tetrahedron Lett. 1985; 26: 5299
• 22a Hochstein FA. J. Am. Chem. Soc. 1955; 77: 5744
• 22b Svoboda GH. J. Am. Pharm. Assoc. 1957; 46: 508
• 22c Shimizu M, Uchimaru F. Chem. Pharm. Bull. 1958; 6: 324
• 22d Patel MB, Poisson J, Pousset JL, Rowson JM. J. Pharm. Pharmacol. 1964; 16: 163
• 22e Maloney EM, Farnsworth NR, Blomster RN, Abraham DJ, Sharkey AG. Jr. J. Pharm. Sci. 1965; 54: 1166
• 22f Chan KC. Phytochemistry 1969; 8: 219
• 22g Kim HK, Blomster RN, Fong HH. S, Farnsworth NR. Econ. Bot. 1970; 24: 42
• 22h Merlini L, Mondelli R, Nasini G, Hesse M. Tetrahedron 1970; 26: 2259
• 22i Phillipson JD, Hemingway SR. Phytochemistry 1973; 12: 1481
• 22j Habib MS, Court WE. Phytochemistry 1974; 13: 661
• 22k Timmins P, Court WE. Planta Med. 1976; 29: 283
• 22l Dutta SC, Bhattacharya SK, Ray AB. Planta Med. 1976; 30: 86
• 22m Akinloye BA, Court WE. Planta Med. 1979; 37: 361
• 22n Ponglux D, Supavita T, Verpoorte R, Phillipson JD. Phytochemistry 1980; 19: 2013
• 22o Weiming C, Yaping Y, Xiaotian L. Planta Med. 1983; 49: 62
• 22p Phillipson JD, Supavita N. Phytochemistry 1983; 22: 1809
• 22q Guillaume D, Morfaux AM, Richard B, Massiot G, Le Men-Olivier L, Pusset J, Sevenet T. Phytochemistry 1984; 23: 2407
• 22r Martinez JA, Gomez C, Santana T, Velez H. Planta Med. 1989; 55: 283
• 22s Laus G, Brossner D, Keplinger K. Phytochemistry 1997; 45: 855
• 22t Sheludko Y, Gerasimenko I, Kolshorn H, Stöckigt J. J. Nat. Prod. 2002; 65: 1006
• 23a Wenkert E, Wickberg B, Leicht CL. J. Am. Chem. Soc. 1961; 83: 5037
• 23b Shamma M, Richey JM. J. Am. Chem. Soc. 1963; 85: 2507
• 24a Sichaem J, Surapinit S, Siripong P.-P, Khumkratok S, Jong-aramruang J, Tip-pyang S. Fitoterapia 2010; 81: 830
• 24b Surapinita S, Sichaemc J, Tip-pyang S. Nat. Prod. Commun. 2018; 13: 33
• 25a Shigemori H, Kagata T, Ishiyama H, Morah F, Ohsaki A, Kobayashi J. Chem. Pharm. Bull. 2003; 51: 58
• 25b Ata A, Udenigwe CC, Matochko W, Holloway P, Eze MO, Uzoegwu PN. Nat. Prod. Commun. 2009; 4: 1185
• 25c Li Q, Zhang Y, Wu B, Qu H. Eur. J. Mass Spectrom. 2011; 17: 277
• 25d Liu Q, Chen A, Jiang Z, Ma Y, Tang J, Xu W, Liu Y, Fu Y. Chin. J. Org. Chem. 2018; 38: 1833
• 25e Liu Y.-P, Chen A.-H, Li R.-H, Yang H.-W, Bao H.-N, Lai L, Zong K, Fu Y.-H. Nat. Prod. Commun. 2017; 12: 369

Isolation of apogeissoschizine:
• 26a da Silva e Silva JV, Brigido HP. C, Oliveira de Albuquerque KC, Carvalho JM, Reis JF, Faria LV, Coelho-Ferreira MR, Silveira FT, da Silva Carneiro A, Percário S, do Rosário Marinho AM, Dolabela MF. Molecules 2019; 24: 785
• 26b Shi B.-B, Chen J, Bao M.-F, Zeng Y, Cai X.-H. Phytochemistry 2019; 166: 112060
• 27 Meyers AI, Sohda T, Loewe MF. J. Org. Chem. 1986; 51: 3108
• 28a Rapoport H, Windgasson RJ. Jr, Hughes NA, Onak TP. J. Am. Chem. Soc. 1960; 82: 4404
• 28b Janot M.-M. Tetrahedron 1961; 14: 113
• 28c Mehri H, Sciamama M, Plat T, Sevenet T, Pusset J. Ann. Pharm. Fr. 1984; 42: 145
• 29 Tao Y, Chen L, Yan J. J. Ethnopharmacol. 2020; 258: 112912
• 30 Kawai H, Kuroyanagi M, Ueno A. Chem. Pharm. Bull. 1988; 36: 3664
• 31 Yamamoto H, Katano N, Ooi A, Inoue K. Phytochemistry 2000; 53: 7