Synthesis of the Cyclohexane Fragment Peculiar to Enacyloxins: Study of Its Assembly and Protective Groups Removal

Orane Christin; Emmanuel Roulland

doi:10.1055/s-0042-1751567

Synthesis, Table of Contents

Synthesis 2024; 56(14): 2239-2246
DOI: 10.1055/s-0042-1751567

paper

Synthesis of the Cyclohexane Fragment Peculiar to Enacyloxins: Study of Its Assembly and Protective Groups Removal

Orane Christin

,

Emmanuel Roulland∗

Abstract

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Abstract

The enantioselective synthesis of the protected (1S,3R,4S)-3,4-dihydroxycyclohexane-1-carboxylic acid moiety shared among all members of the enacyloxin family has been successfully accomplished. Having obtained this fragment, we devised assembly conditions using models that mimic the enacyloxin acyl chain. Additionally, we assessed conditions for the removal of protective groups, aiming to avoid previously reported detrimental ester shifts.

Key words

total synthesis - natural products - ring-closing metathesis - palladium - carbonylation - kinetic reprotonation

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References

References

1a Watanabe T, Sugiyama T, Takahashi M, Shima J, Yamashita K, Izaki K, Furihata K, Seto H. Agric. Biol. Chem. 1990; 54: 259
1b Watanabe T, Sugiyama T, Takahashi M, Shima J, Yamashita K, Izaki K, Furihata K, Seto H. J. Antibiot. 1992; 45: 470
1c Watanabe T, Shima J, Izaki K, Sugiyama T. J. Antibiot. 1992; 45: 575
1d Watanabe T, Kiyota H, Takeuchi R, Enari K, Oritani T. Heterocycl. Commun. 2001; 7: 313
1e Fujimori T, Nakayama O, Kiyota H, Kamijima Y.-i, Watanabe T, Oritani T. Heterocycl. Commun. 2001; 7: 327
1f Takeuchi R, Kiyota H, Yaosaka M, Watanabe T, Enari K, Sugiyama T, Oritani T. J. Chem. Soc., Perkin Trans. 1 2001; 2676

2a Watanabe T, Izaki K, Takahashi H. J. Antibiot. 1982; 35: 1141
2b Watanabe T, Izaki K, Takahashi H. J. Antibiot. 1982; 35: 1148

3 Furukawa H, Kiyota H, Yamada T, Yaosaka M, Takeuchi R, Watanabe T, Kuwahara S. Chem. Biodiversity 2007; 4: 1601
4 Mahenthiralingam E, Song L, Sass A, White J, Wilmot C, Marchbank A, Boaisha O, Paine J, Knight D, Challis GL. Chem. Biol. 2011; 18: 665
5 Ross C, Opel V, Scherlach K, Hertweck C. Mycoses 2014; 57 (Suppl. 03) 48
6 Heath NL, Rowlands RS, Webster G, Mahenthiralingam E, Beeton ML. J. Appl. Microbiol. 2020; 130: 1546
7 Clough B, Rangachari K, Strath M, Preiser PR, Wilson RJ. M. Protist 1999; 150: 189

8a Parmeggiani A, Krab IM, Watanabe T, Nielsen RC, Dahlberg C, Nyborg J, Nissen P. J. Biol. Chem. 2006; 281: 2893
8b Cetin R, Krab IM, Anborgh PH, Cool RH, Watanabe T, Sugiyama T, Izaki K, Parmeggiani A. EMBO J. 1996; 15: 2604

9 Norsikian S, Tresse C, François-Eude M, Jeanne-Julien L, Masson G, Servajean V, Genta-Jouve G, Beau J.-M, Roulland E. Angew. Chem. Int. Ed. 2020; 59: 6612
10 Christin O, Roulland E. Org. Lett. 2023; 25: 6869
11 Sugiyama T, Kiyota H, Watanabe T, Oritani T. Nat. Prod. Res. 2005; 19: 581
12 Saito A, Igarashi W, Furukawa H, Yamada T, Kuwahara S, Kiyota H. Biosci., Biotechnol., Biochem. 2014; 78: 766
13 Hodgson DM, Chung YK, Nuzzo I, Freixas G, Kulikiewicz KK, Cleator E, Paris J.-M. J. Am. Chem. Soc. 2007; 129: 4456
14 Roulland E, Ermolenko MS. Org. Lett. 2005; 7: 2225
15 Ilardi EA, Stivala CE, Zakarian A. Org. Lett. 2008; 10: 1727
16 Arthuis M, Lecup A, Roulland E. Chem. Commun. 2010; 46: 7810

17a Zimmerman HE. Acc. Chem. Res. 1987; 20: 263
17b Zimmerman HE, Mariano PS. J. Am. Chem. Soc. 1968; 90: 6091

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