Total Syntheses of Spinosyn A

Xinpei Cai; Yu Bai; Mingji Dai

doi:10.1055/s-0037-1610249

Synlett, Table of Contents

Synlett 2018; 29(20): 2623-2632
DOI: 10.1055/s-0037-1610249

account

Total Syntheses of Spinosyn A

Xinpei Cai

,

Yu Bai

,

Mingji Dai *

Department of Chemistry, Center for Cancer Research, and Institute for Drug Discovery, Purdue University, West Lafayette, Indiana 47907, USA Email: mjdai@purdue.edu

› Author Affiliations

Abstract

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Abstract

Spinosyn A is an important polycyclic natural product with impressive insecticidal activity and has been used worldwide in agriculture as the major component of Spinosad. Herein, four chemical total syntheses of spinosyn A are summarized. Its biosynthesis and a chemoenzymatic total synthesis are discussed as well.

1 Biosynthesis

2 The Evans Synthesis

3 The Paquette Synthesis

4 The Roush Synthesis

5 The Liu Synthesis

6 The Dai Synthesis

7 Conclusions

Key words

spinosyn A - total synthesis - natural product - insecticide - Spinosad

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References

References

1a Cantrell CL. Dayan FE. Duke SO. J. Nat. Prod. 2012; 75: 1231
1b Rimando AM. Duke SO. Natural Products for Pest Management . In Natural Products for Pest Management . American Chemical Society; Washington, DC: 2006: 2-21

2a Sparks TC. Crouse GD. Durst G. Pest Manage. Sci. 2001; 57: 896
2b Kirst HA. J. Antibiot. 2010; 63: 101

3 Kirst HA. Michel KH. Martin JW. Creemer LC. Chio EH. Yao RC. Nakatsukasa WM. Boeck LD. Occolowitz JL. Paschal JW. Deeter JB. Jones ND. Thompson GD. Tetrahedron Lett. 1991; 32: 4839

4a Roe RM. Young HP. Iwasa T. Wyss CF. Stumpf CF. Sparks TC. Watson GB. Sheets JJ. Thompson GD. Pestic. Biochem. Physiol. 2010; 96: 8
4b Sparks T. Dripps JE. Watson GB. Paroonagian D. Pestic. Biochem. Physiol. 2012; 102: 1
4c Su T. Cheng ML. J. Med. Entomol. 2014; 51: 428
4d Rehan A. Freed S. Crop Prot. 2014; 56: 10
4e Khan HA. A. Akram W. Shad SA. Acta Trop. 2014; 130: 148

5a Martynow JG. Kirst HA. J. Org. Chem. 1994; 59: 1548
5b De Amicis CV. Graupner PR. Erickson JA. Paschal JW. Kirst HA. Creemer LC. Fanwick PE. J. Org. Chem. 2001; 66: 8431
5c Lewer P. Hahn DR. Karr LL. Duebelbeis DO. Gilbert JR. Crouse GD. Worden T. Sparks TC. Edwards PM. R. Graupner PR. Bioorg. Med. Chem. 2009; 17: 4185
5d Daeuble J. Sparks TC. Johnson P. Graupner PR. Bioorg. Med. Chem. 2009; 17: 4197
5e Oliver MP. Crouse GD. Demeter DA. Sparks TC. J. Agric. Food Chem. 2015; 63: 5571

6a Sparks TC. Crouse GD. Dripps JE. Anzeveno P. Martynow J. DeAmicis CV. Gifford J. J. Comput.-Aided Mol. Des. 2008; 22: 393
6b Dripps JE. Boucher RE. Chloridis A. Cleveland CB. DeAmicis CV. Gomez LE. Paroonagian DL. Pavan LA. Sparks TC. Watson GB. The Spinosyn Insecticides . In Green Trends in Insect Control . Lopez O. Fernadez-Bolanos JG. RSC Publishing; Cambridge: 2011: 163-212

7a Tietze LF. Schützenmeister N. Grube A. Scheffer T. Baag MM. Granitzka M. Stalke D. Eur. J. Org. Chem. 2012; 5748
7b Tietze LF. Dietz S. Schützenmeister N. Hierold J. Scheffer T. Baag MM. Eur. J. Org. Chem. 2013; 7305

8a Waldron C. Matsushima P. Rosteck PR. Jr. Broughton MC. Turner J. Madduri K. Crawford KP. Merlo DJ. Baltz RH. Chem. Biol. 2001; 8: 487
8b Martin CJ. Timoney MC. Sheridan RM. Kendrew SG. Wilkinson B. Staunton J. Leadlay PF. Org. Biomol. Chem. 2003; 1: 4144

9 Kim HJ. Pongdee R. Wu Q. Lin H. Liu H.-w. J. Am. Chem. Soc. 2007; 129: 14582

10a Kim HJ. Ruszczycky MW. Choi S.-h. Liu Y.-n. Liu H.-w. Nature 2011; 473: 109
10b Jeon B.-s. Wang S.-A. Ruszczycky MW. Liu H.-w. Chem. Rev. 2017; 117: 5367

11a Patel A. Chen Z. Yang Z. Gutiérrez O. Liu H.-w. Houk KN. Singleton DA. J. Am. Chem. Soc. 2016; 138: 3631
11b Medvedev MG. Zeifman AA. Novikov FN. Bushmarinov IS. Stroganov OV. Titov IY. Chilov GG. Svitanko IV. J. Am. Chem. Soc. 2017; 139: 3942
11c Jeon B.-s. Ruszczycky MW. Russell WK. Lin G.-M. Kim N. Choi S.-h. Wang S-A. Liu Y.-n. Patrick JW. Russell DH. Liu H.-w. Proc. Natl. Acad. Sci. U.S.A. 2017; 114: 10408
11d Yang Z. Yang S. Yu P. Li Y. Doubleday C. Park J. Patel A. Jeon B.-s. Russell WK. Liu H.-w. Russell DH. Houk KN. Proc. Natl. Aca. Sci. U.S.A. 2018; 115: E848

12 Kim HJ. White-Phillip JA. Ogasawara Y. Shin N. Isiorho EA. Liu H.-w. J. Am. Chem. Soc. 2010; 132: 2901

13a Zhao Z. Hong L. Liu H.-w. J. Am. Chem. Soc. 2005; 127: 7692
13b Hong L. Zhao Z. Liu H.-w. J. Am. Chem. Soc. 2006; 128: 14262
13c Zhao Z. Hong L. Melançon III CE. Zhang H. Liu H.-w. J. Am. Chem. Soc. 2008; 130: 4954

14 Evans DA. Black WC. J. Am. Chem. Soc. 1993; 115: 4497

15a Paquette LA. Gao Z. Ni Z. Smith GF. J. Am. Chem. Soc. 1998; 120: 2543
15b Paquette LA. Collado I. Purdie M. J. Am. Chem. Soc. 1998; 120: 2553

16a Mergott DJ. Frank SA. Roush WR. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 11955
16b Winbush SM. Mergott DJ. Roush WR. J. Org. Chem. 2008; 73: 1818

17 Kim HJ. Choi S.-h. Jeon B.-s. Kim N. Pongdee R. Wu Q. Liu H.-w. Angew. Chem. Int. Ed. 2014; 53: 13553
18 Bai Y. Shen X. Li Y. Dai M. J. Am. Chem. Soc. 2016; 138: 10838
19 Yu B. Acc. Chem. Res. 2018; 51: 507

20a Loskot SA. Romney DK. Arnold FH. Stoltz BM. J. Am. Chem. Soc. 2017; 139: 10196
20b Zhang X. King-Smith E. Renata H. Angew. Chem. Int. Ed. 2018; 57: 5037
20c Zwick CR. III. Renata H. J. Am. Chem. Soc. 2018; 140: 1165
20d King-Smith E. Zwick III CR. Renata H. Biochemistry 2018; 57: 403