Total Synthesis of Natural Terpenoids: Inspired but Not Limited by Biohypothesis

Abstract

This account describes our studies on the total synthesis of several natural terpenoids based on our modified biosynthetic hypothesis. Compared to the originally proposed biosynthetic hypothesis, the modified ones proved to be more practicable for the formation of hispidanin A, a dimeric diterpenoid, and sarcandrolide J and shizukaol D, two dimeric sesquiterpenoids, from a viewpoint of chemical reactivity. Moreover, a cascade reaction involving intermolecular and intramolecular cycloaddition was facilitated to expeditiously accumulate molecular complexity in the total synthesis of bolivianine, a sesterterpenoid, on the basis of a modified biohypothesis.

1 Introduction

2 Total Synthesis of Hispidanin A

3 Total Syntheses of Bolivianine and Isobolivianine

4 Total Syntheses of Sarcandrolide J and Shizukaol D

5 Conclusion

Key words

terpenoids - total synthesis - biohypothesis - cascade - ­cycloaddition - cyclization

• References


For recent review articles, see:
• 1a Hugelshofer C. Magauer T. Org. Biomol. Chem. 2017; 15: 12
• 1b Zhu G. Wadavrao SB. Liu B. Chem. Rec. 2017; 17: 584
• 1c Brill ZG. Condakes ML. Ting CP. Maimone TJ. Chem. Rev. 2017; 117: 11753
• 1d Qiao T. Liang G. Sci. China Chem. 2016; 59: 1142
• 1e Urabe D. Asaba T. Inoue M. Chem. Rev. 2015; 115: 9207
• 2 Walsh CT. Tang Y. Natural Product Biosynthesis: Chemical Logic and Enzymatic Machinery . RSC Publishing; Croydon: 2017. 195
• 3a Craig RA. Stoltz BM. Chem. Rev. 2017; 117: 7878
• 3b Li C. Jones AX. Lei X. Nat. Prod. Rep. 2016; 33: 602
• 4 Huang B. Xiao C.-J. Huang Z.-Y. Tian X.-Y. Cheng X. Dong X. Jiang B. Org. Lett. 2014; 16: 3552
• 5 Deng H. Cao W. Zhang Z. Liu B. Org. Biomol. Chem. 2016; 14: 6225
• 6a Ulubelen A. Topcu G. Chen S. Cai P. Snyder JK. J.Org. Chem. 1991; 56: 7354
• 6b Ulubelen A. Topcu G. Tan N. Phytochemistry 1995; 40: 1473
• 7 Wang X.-N. Bashyal BP. Wijeratne EM. K. U’Ren JM. Liu MX. Gunatilaka MK. Arnold AE. Gunatilaka AA. L. J. Nat. Prod. 2011; 74: 2052
• 8 Zhou J. Pan L. Li Q. Pu J. Yao P. Zhu M. Banas JA. Zhang H. Sun H. Org. Biomol. Chem. 2012; 10: 5039
• 9 Streuff J. Gansauer A. Angew. Chem. Int. Ed. 2015; 54: 14232
• 10 Miyabe H. Kawashima A. Yoshioka E. Kohtani S. Chem. Eur. J. 2017; 23: 6225
• 11 Gordon HL. Freeman S. Hudlicky T. Synlett 2005; 2911
• 12a Deng HH. Cao W. Liu R. Zhang Y. Liu B. Angew. Chem. Int. Ed. 2017; 56: 5849
• 12b Nishikado H. Nakatsuji H. Ueno K. Nagase R. Tanabe Y. Synlett 2010; 2087
• 13 Li F. Tu Q. Chen S. Zhu L. Lan Y. Gong J. Yang Z. Angew. Chem. Int. Ed. 2017; 56: 5844
• 14 Acebey L. Sauvain M. Beck S. Moulis C. Gimenez A. Jullian V. Org. Lett. 2007; 9: 4693
• 15 Lorenzo D. Loayza I. Dellacassa E. Flavour Fragr. J. 2003; 18: 32
• 16a Acebey L. Jullian V. Sereno D. Chevalley S. Estevez Y. Moulis C. Beck S. Valentin A. Gimenez A. Sauvain M. Planta Med. 2010; 76: 365
• 16b Trentin AP. Santos AR. S. Guedes A. Pizzolatti MG. Yunes RA. Calixto JB. Planta Med. 1999; 65: 517
• 16c Bohlmann F. Zdero C. King RM. Robinson H. Phytochemistry 1980; 19: 689
• 17a Yue G. Yang L. Yuan C. Jiang X. Liu B. Org. Lett. 2011; 13: 5406
• 17b Yue G. Yang L. Yuan C. Du B. Liu B. Tetrahedron 2012; 68: 9624
• 17c Yue G. Yang L. Yuan C. Du B. Liu B. Chin. J. Org. Chem. 2013; 33: 90
• 18a Fenton TW. Schwaebisch D. Mayweg AV. W. Lee V. Adlington RM. Baldwin JE. Synlett 2007; 2679
• 18b Fenlon TW. Jones MW. Adlington RM. Lee V. Org. Biomol. Chem. 2013; 11: 8026
• 18c Qian S. Zhao G. Synlett 2011; 722
• 18d Qian S. Zhao G. Chem. Commun. 2012; 48: 3530
• 18e Qian S. Zhao G. Tetrahedron 2013; 69: 11169
• 18f Ramesh S. Mehta G. Tetrahedron Lett. 2015; 56: 3941
• 19a Yuan C. Du B. Yang L. Liu B. J. Am. Chem. Soc. 2013; 135: 9291
• 19b Yang Y. Li J. Du B. Yuan C. Liu B. Qin S. Chem. Commun. 2015; 51: 6179
• 19c Du B. Yuan C. Yu T. Yang L. Yang Y. Liu B. Qin S. Chem. Eur. J. 2014; 20: 2613
• 20 Unpublished results.
• 21 Li J.-P. Yuan C.-C. Du B. Liu B. Chin. Chem. Lett. 2017; 28: 113
• 22 Liu B. Yuan C. Du B. In Strategies and Tactics in Organic Synthesis . Vol. 13. Harmata M. Elsevier; Kidlington: 2017: 161
• 23 Kawabata J. Fukushi Y. Tahara S. Mizutani J. Phytochemistry 1990; 29: 2332

For review articles see:
• 24a Cao C.-M. Peng Y. Shi Q.-W. Xiao P.-G. Chem. Biodiversity 2008; 5: 219
• 24b Xu Y.-J. Chem. Biodiversity 2013; 10: 1754
• 24c Wang A.-R. Song H.-C. An H.-M. Huang Q. Luo X. Dong J.-Y. Chem. Biodiversity 2015; 12: 451
• 24d Fan Y.-Y. Gao X.-H. Yue J.-M. Sci. China Chem. 2016; 59: 1126
• 25 Kwon OE. Lee HS. Lee SW. Bae K. Kim K. Hayashi M. Rho M.-C. Kim Y.-K. J. Ethnopharmacol. 2006; 104: 270
• 26 Zhou B. Wu Y. Dalal S. Merino EF. Liu Q.-F. Xu C.-H. Yuan T. Ding J. Kingston DG. I. Cassera MB. Yue J.-M. J. Nat. Prod. 2017; 80: 96
• 27a Lu Y.-S. Peng X.-S. Org. Lett. 2011; 13: 2940
• 27b Liu Y. Nan F.-J. Tetrahedron Lett. 2010; 51: 1374
• 27c Zhang H. Nan F. Chin. J. Chem. 2013; 31: 84
• 27d Yang L. Yue G. Yuan C. Du B. Deng H. Liu B. Synlett 2014; 25: 2471
• 28 Uchida M. Kusano G. Kondo Y. Nozoe S. Heterocycles 1978; 9: 139
• 29a Takeda K. Ishii H. Tozyo T. Minato H. J. Chem. Soc. C: Organic 1969; 1920
• 29b Takeda K. Ikuta M. Miyawaki M. Tetrahedron 1964; 20: 2991
• 29c Ishii H. Tozyo T. Nakamura M. Takeda K. Tetrahedron 1968; 24: 625
• 30 Yang S.-P. Gao Z.-B. Wang F.-D. Liao S.-G. Chen H.-D. Zhang C.-R. Hu G.-Y. Yue J.-M. Org. Lett. 2007; 9: 903
• 31 Kawabata J. Mizutani J. Phytochemistry 1992; 31: 1293
• 32a Hu R. Yan H. Hao X. Liu H. Wu J. PLoS ONE 2013; 8: e73527
• 32b Tang L. Zhu H. Yang X. Xie F. Peng J. Jiang D. Xie J. Qi M. Yu L. PLoS ONE 2015; 11: e0152012
• 33 Ni G. Zhang H. Liu H.-C. Yang S.-P. Geng M.-Y. Yue J.-M. Tetrahedron 2013; 69: 564
• 34 Yuan C. Du B. Deng H. Man Y. Liu B. Angew. Chem. Int. Ed. 2017; 56: 637