Catalytic Asymmetric Approach to the Naturally Occurring Clavine Alkaloid (+)-Lysergine

Mrinal K. Das; Kundan Shaw; Saikat Chaudhuri; Debabrata Mondal; Alakesh Bisai

doi:10.1055/a-2385-5110

Synthesis, Inhaltsverzeichnis

Synthesis 2025; 57(02): 407-416
DOI: 10.1055/a-2385-5110

paper

Special Topic Dedicated to Prof. H. Ila

Catalytic Asymmetric Approach to the Naturally Occurring Clavine Alkaloid (+)-Lysergine

Mrinal K. Das‡

^aDepartment of Chemistry, Karimpur Pannadevi College, Kalyani University, West Bengal, India

,

Kundan Shaw‡

^bDepartment of Chemical Sciences, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462 066, Madhya Pradesh, India

,

Saikat Chaudhuri

^cOrganic and Bio-organic Chemistry Laboratory, CSIR-CLRI Chennai, Adyar, Chennai, 600020, India

,

Debabrata Mondal

^dDepartment of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, Nadia 741 246, West Bengal, India

,

Alakesh Bisai ∗

^bDepartment of Chemical Sciences, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462 066, Madhya Pradesh, India

^dDepartment of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, Nadia 741 246, West Bengal, India

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Abstract

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This work is dedicated respectfully to Prof. H. Ila, JNCASR Bangalore, India.

Abstract

An efficient asymmetric approach to the ergot alkaloids has been achieved via a highly regioselective Heck cyclization. Asymmetric induction of the key intermediate was achieved via a catalytic enantioselective α-aminoxylation catalyzed by d-proline (98% ee). Utilizing the aforementioned strategy, formal total synthesis of the ergot alkaloids (+)-lysergine and (+)-isolysergine has been achieved. Importantly, an asymmetric approach to the unnatural analogues (–)-lysergine and (–)-isolysergine has also been achieved via catalytic enantioselective α-aminoxylation using l-proline.

Key words

asymmetric total synthesis - regioselective Heck cyclization - lysergine - α-aminoxylation - ergot alkaloids

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Referenzen

References

1a Ninomiya I, Kiguchi T. In The Alkaloids, Vol. 38. Brossi A. Academic Press; San Diego: 1990: 1-156
1b Somei M, Yokoyama Y, Murakami Y, Ninomiya I, Kiguchi T, Naito T. In The Alkaloids, Vol. 54. Cordell GA. Academic Press; San Diego: 2000: 191-257

2a Floss HG. Tetrahedron 1976; 32: 873
2b Schwarzer DD, Gritsch PJ, Gaich T. Synlett 2013; 24: 1025

Reviews:

3a Wallwey C, Li S.-M. Nat. Prod. Rep. 2011; 28: 496
3b Liu H, Jia Y. Nat. Prod. Rep. 2017; 34: 411

4a Sinz A. Pharm. Unserer Zeit 2008; 37: 306
4b Gröcer D, Floss HG. In The Alkaloids, Vol. 50. Cordell GA. Academic Press; San Diego: 1998: 171-218

5 Schardl CL, Panaccione DG, Tudzynski P. In The Alkaloids, Vol. 63. Cordell GA. Academic Press; San Diego: 2006: 45-86

6a Jakubczyk D, Caputi L, Hatsch A, Nielson CA. F, Diefenbacher M, Klein J, Molt A, Schröder H, Cheng JZ, Naesby M, O’Conner SE. Angew. Chem. Int. Ed. 2015; 54: 5117
6b Jakubczyk D, Caputi L, Stevenson CE. M, Lawson DM, O’Conner SE. Chem. Commun. 2016; 52: 14306
6c Jakubczyk D, Cheng JZ, O’Connor SE. Nat. Prod. Rep. 2014; 31: 1328
6d Young CA, Schardl CL, Panaccione DG, Florea S, Takach JE, Charlton ND, Moore N, Webb JS, Jaromczyk J. Toxins 2015; 7: 1273

7a Kornfeld EC, Fornefeld EJ, Kline GB, Mann MJ, Morrison D, Jones RG, Woodward RB. J. Am. Chem. Soc. 1956; 78: 3087
7b Oppolzer W, Francotte E, Battig K. Helv. Chim. Acta 1981; 64: 478
7c Rebek J, Tai DF, Shue Y.-K. J. Am. Chem. Soc. 1984; 106: 1813
7d Hendrickson JB, Wang J. Org. Lett. 2004; 6: 3
7e Moldvai I, Temesvári-Major E, Incze M, Szentirmay É, Gács-Baitz E, Szántay C. J. Org. Chem. 2004; 69: 5993
7f Inuki S, Oishi S, Fujii N, Ohno H. Org. Lett. 2008; 10: 5239
7g Inuki S, Iwata A, Oishi S, Fujii N, Ohno H. J. Org. Chem. 2011; 76: 2072
7h Inuki S, Oishi S, Fujii N, Ohno H. Org. Lett. 2011; 13: 2145
7i Iwata A, Inuki S, Oishi S, Fujii N, Ohno H. J. Org. Chem. 2011; 76: 5506
7j Liu Q, Jia Y. Org. Lett. 2011; 13: 4810
7k Umezaki S, Yokoshima S, Fukuyama T. Org. Lett. 2013; 15: 4230
7l Romanini S, Galletti E, Caruana L, Mazzanti A, Himo F, Santoro S, Fochi M, Bernardi L. Chem. Eur. J. 2015; 21: 17578
7m Yuan H, Guo Z, Luo T. Org. Lett. 2017; 19: 624
7n Milde B, Pawliczek M, Jones PG, Werz DB. Org. Lett. 2017; 19: 1914
7o Bhunia S, Chaudhuri S, De S, Babu KN, Bisai A. Org. Biomol. Chem. 2018; 16: 2427

8a Bhunia S, Chaudhuri S, Bisai A. Chem. Eur. J. 2017; 23: 11234

For a biomimetic approach, see:

8b Chaudhuri S, Bhunia S, Roy A, Das MK, Bisai A. Org. Lett. 2018; 20: 288
8c Diotallevi F, Bartoccini F, Piersanti G. Eur. J. Org. Chem. 2024; 27: e202400035

9a For utilization of an α-aminoxylation reaction in the total synthesis of (+)-cycloclavine, see: Chaudhuri S, Ghosh S, Bhunia S, Bisai A. Chem. Commun. 2018; 54: 940

For a biomimetic approach, see:

9b Kimura M, Futamata M, Mukai R, Tamaru YJ. Chem. Soc. 2005; 127: 4592

10a For L-proline-catalyzed α-aminoxylation of aldehydes, see: Zhong G. Angew. Chem. Int. Ed. 2003; 42: 4247

For l-proline-catalyzed α-amination of aldehydes, see:

10b List B. J. Am. Chem. Soc. 2002; 124: 5656
10c Bøgevig A, Juhl K, Kumaragurubaran N, Zhuang W, Jørgensen KA. Angew. Chem. Int. Ed. 2002; 41: 1790

11 For α-aminoxylation and Horner–Wadsworth–Emmons olefination of aldehydes, see: Kondekar NB, Kumar P. Org. Lett. 2009; 11: 2611

12a Hayashi Y, Shoji M, Ishikawa H, Yamaguchi J, Tamura T, Imai H, Nishigaya Y, Takabe K, Kakeya H, Osada H. Angew. Chem. Int. Ed. 2008; 47: 6657
12b Yadav JS, Ramesh K, Reddy UV. S, Reddy BV. S, Ghamdi AA. K. A. Tetrahedron Lett. 2011; 52: 2943

13 Mitsunobu reaction of δ-amino alcohols 18a, 18b using diethyl azodicarboxylate (DEAD) and PPh₃ in toluene yielded compounds 20a, 20b in 56–59% isolated yield.
14 Lu Y, Yuan H, Zhou S, Luo T. Org. Lett. 2017; 19: 620

For leading references for Pd-catalyzed intramolecular Heck cyclization for the synthesis of natural products, see:

15a Zhang M, Huang X, Shen L, Qin Y. J. Am. Chem. Soc. 2009; 131: 6013
15b Wu J, Becerril J, Lian Y, Davies HL. M, Porco JA. Jr, Panek JS. Angew. Chem. Int. Ed. 2011; 50: 5938
15c Chen J.-Q, Xie J.-H, Bao D.-H, Liu S, Zhou Q.-L. Org. Lett. 2012; 14: 2714
15d Ren W, Wang Q, Zhu J. Angew. Chem. Int. Ed. 2014; 53: 1818 ; and references cited

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