Total Synthesis of Asperchalasine A

Xianwen Long; Yiming Ding; Hai Wu; Jun Deng

doi:10.1055/s-0039-1691500

Synlett, Table of Contents

Synlett 2020; 31(04): 301-308
DOI: 10.1055/s-0039-1691500

synpacts

Total Synthesis of Asperchalasine A

Xianwen Long

^aState Key Laboratory of Phytochemistry and Plant Resources in West China, and Yunnan Key Laboratory of Natural Medicinal Chemistry, Kunming Institute of Botany, Chinese Academy of Sciences, 132 Lanhei Road, Kunming 650201, P. R. of China Email: dengjun@mail.kib.ac.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100049 P. R. of China

,

Yiming Ding

^aState Key Laboratory of Phytochemistry and Plant Resources in West China, and Yunnan Key Laboratory of Natural Medicinal Chemistry, Kunming Institute of Botany, Chinese Academy of Sciences, 132 Lanhei Road, Kunming 650201, P. R. of China Email: dengjun@mail.kib.ac.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100049 P. R. of China

,

Hai Wu

^aState Key Laboratory of Phytochemistry and Plant Resources in West China, and Yunnan Key Laboratory of Natural Medicinal Chemistry, Kunming Institute of Botany, Chinese Academy of Sciences, 132 Lanhei Road, Kunming 650201, P. R. of China Email: dengjun@mail.kib.ac.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100049 P. R. of China

,

Jun Deng∗

^aState Key Laboratory of Phytochemistry and Plant Resources in West China, and Yunnan Key Laboratory of Natural Medicinal Chemistry, Kunming Institute of Botany, Chinese Academy of Sciences, 132 Lanhei Road, Kunming 650201, P. R. of China Email: dengjun@mail.kib.ac.cn

› Author Affiliations

Abstract

All articles of this category

Abstract

Here we briefly reviewed recent synthetic progress toward cytochalasan trimer, asperchalasine A by Tang, Trauner and our group. This process features a highly stereoselective intermolecular Diels–Alder reaction and a HWE or RCM macrocyclization to establish the key monomer aspochalasin B. A late-stage biomimetic oxidative dearomatization of triphenol and subsequent [5+2] cycloaddition cascade furnished asperchalasine A. We anticipate that this key reaction could also be used for the synthesis of other merocytochalasans, and provide some insight into the biosynthetic connections of merocytochalasans.
1 Introduction
2 Total Synthesis of Aspochalasin B
3 Total Synthesis of Asperchalasine A
4 Conclusions

Key words

biomimetic synthesis - [5+2] cycloaddition - natural products - total synthesis - dimerization

Full Text

References

References
1 Scherlach K, Boettger D, Remme N, Hertweck C. Nat. Prod. Rep. 2010; 27: 869

2a Stork G, Nakahara Y, Nakahara Y, Greenlee WJ. J. Am. Chem. Soc. 1978; 100: 7775
2b Stork G, Nakamura E. J. Am. Chem. Soc. 1983; 105: 5510
2c Thomas EJ, Whitehead JW. F. J. Chem. Soc., Chem. Commun. 1986; 727
2d Dyke H, Sauter R, Steel P, Thomas EJ. J. Chem. Soc., Chem. Commun. 1986; 1447
2e Thomas EJ, Whitehead JW. F. J. Chem. Soc., Perkin Trans. 1 1989; 499
2f Merifield E, Thomas EJ. J. Chem. Soc., Chem. Commun. 1990; 464
2g Merifield E, Thomas EJ. J. Chem. Soc., Perkin Trans. 1 1999; 3269
2h Thomas EJ, Willis M. Org. Biomol. Chem. 2014; 12: 7537
2i Vedejs E, Rodgers JD, Wittenberger SJ. J. Am. Chem. Soc. 1988; 110: 4822
2j Trost BM, Ohmori M, Boyd SA, Okawara H, Brickner SJ. J. Am. Chem. Soc. 1989; 111: 8281
2k Auerbach J, Weinreb SM. J. Org. Chem. 1975; 40: 3311
2l Hensel MJ, Palmer JT, Learn KS, Fuchs PL. Synth. Commun. 1986; 16: 1297
2m Boutellier M, Wallach D, Tamm C. Helv. Chim. Acta 1993; 76: 2515
2n Haidle AM, Myers AG. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 12048
2o Canham SM, Overman LE, Tanis PS. Tetrahedron 2011; 67: 9837
2p Tian C, Lei XG, Wang YH, Dong Z, Liu G, Tang YF. Angew. Chem. Int. Ed. 2016; 55: 6992

For isolation of merocytochalasans, see:

3a Zhu H, Chen C, Xue Y, Tong Q, Li XN, Chen X, Wang J, Yao G, Luo Z, Zhang Y. Angew. Chem. Int. Ed. 2015; 54: 13374
3b Lin Z, Ma X, Wei H, Li D, Gu Q, Zhu T. RSC Adv. 2015; 5: 35262
3c Zhu H, Chen C, Tong Q, Li XN, Yang J, Xue Y, Luo Z, Wang J, Yao G, Zhang Y. Angew. Chem. Int. Ed. 2016; 55: 3486
3d Zhu H, Chen C, Tong Q, Yang J, Wei G, Xue Y, Luo Z, Wang J, Luo Z, Zhang Y. Angew. Chem. Int. Ed. 2017; 56: 5242
3e Wu D, Tong Q, Zhang X, Zhou P, Dai C, Wang J, Chen C, Zhu H, Zhang Y. Org. Lett. 2019; 21: 1026

4a Ellerbrock P, Armanino N, Trauner D. Angew. Chem. Int. Ed. 2014; 53: 13414
4b Ellerbrock P, Armanino N, Ilg MK, Webster R, Trauner D. Nat. Chem. 2015; 7: 879

For isolation of aspochalasin B, see:

5a Keller-Schierlein W, Kupfer E. Helv. Chim. Acta 1979; 62: 1501
5b Sekita S, Yoshihira K, Natori S, Harada F, Iida K, Yahara I. J. Pharmacobio-Dyn. 1985; 8: 906

For recent syntheses of aspochalasin B, see:

6a Bao R, Tian C, Zhang H, Wang Z, Dong Z, Li Y, Gao M, Zhang H, Liu G, Tang Y. Angew. Chem. Int. Ed. 2018; 57: 14216
6b Long X, Ding Y, Deng J. Angew. Chem. Int. Ed. 2018; 57: 14221
6c Reyes JR, Winter N, Spessert L, Trauner D. Angew. Chem. Int. Ed. 2018; 57: 15587

7 Deng J, Zhou S, Zhang W, Li J, Li R, Li A. J. Am. Chem. Soc. 2014; 136: 8185
8 Ma Z, Bobbitt JM. J. Org. Chem. 1991; 56: 6110

9a Rathke MW, Nowak M. J. Org. Chem. 1985; 50: 2624
9b Forsyth CJ, Ahmed F, Cink RD, Lee CS. J. Am. Chem. Soc. 1998; 120: 5597
9c Schauer DJ, Helquist P. Synthesis 2006; 3654
9d Larsen BJ, Sun Z, Nagorny P. Org. Lett. 2013; 15: 2998

10 Canham SM, Overman LE, Tanis PS. Tetrahedron 2011; 67: 9837

Acid-promoted isobenzofuran formation:

11a Smith JG, Dibble PW, Sandborn RE. J. Org. Chem. 1986; 51: 3762
11b Nandhikonda P, Heagy MD. Org. Lett. 2010; 12: 4796

Base-promoted isobenzofuran formation:

11c Tobia D, Rickborn B. J. Org. Chem. 1986; 51: 3849
11d Martin C, Mailliet P, Maddaluno J. J. Org. Chem. 2001; 66: 3797

12 Ganguly NC, Dutta S, Datta M. Tetrahedron Lett. 2006; 47: 5807
13 Zhang, X.; Yang, L.; Wang, W.; Wu, Z.; Wang, J.; Sun, W.; Li, X.; Chen, C.; Zhu, H.; Zhang, Y. J. Nat. Prod. 2019, in press; doi: 10.1021/acs.jnatprod.9b00512