The Chiral Pool in the Pictet-Spengler Reaction for the Synthesis of β-Carbolines

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2016 May 31

PMID 27240334

Citations 6

Authors

Renato Dalpozzo

Affiliations

Soon will be listed here.

Abstract

The Pictet-Spengler reaction (PSR) is the reaction of a β-arylethylamine with an aldehyde or ketone, followed by ring closure to give an aza-heterocycle. When the β-arylethylamine is tryptamine, the product is a β-carboline, a widespread skeleton in natural alkaloids. In the natural occurrence, these compounds are generally enantiopure, thus the asymmetric synthesis of these compounds have been attracting the interest of organic chemists. This review aims to give an overview of the asymmetric PSR, in which the chirality arises from optically pure amines or carbonyl compounds both from natural sources and from asymmetric syntheses to assemble the reaction partners.

Citing Articles

Current Status of Indole-Derived Marine Natural Products: Synthetic Approaches and Therapeutic Applications.

Fernandez S, Arnaiz V, Rufo D, Arroyo Y Mar Drugs. 2024; 22(3).

PMID: 38535467 PMC: 10971852. DOI: 10.3390/md22030126.

Stereoselective Synthesis of Benzo[]quinolizidines via Aerobic DDQ-Catalyzed Allylation and Reductive Cyclization.

Jung S, Yoon S, Lee J, Min S ACS Omega. 2022; 7(36):32562-32568.

PMID: 36120044 PMC: 9476524. DOI: 10.1021/acsomega.2c04154.

Enantiodivergent Synthesis of Benzoquinolizidinones from L-Glutamic Acid.

Kuntiyong P, Namborisut D, Phakdeeyothin K, Chatpreecha R, Thammapichai K Molecules. 2021; 26(19).

PMID: 34641410 PMC: 8512815. DOI: 10.3390/molecules26195866.

Synthesis of aza-quaternary centers Pictet-Spengler reactions of ketonitrones.

Lynch-Colameta T, Greta S, Snyder S Chem Sci. 2021; 12(17):6181-6187.

PMID: 33996016 PMC: 8098696. DOI: 10.1039/d1sc00882j.

The Pictet-Spengler Reaction Updates Its Habits.

Calcaterra A, Mangiardi L, Delle Monache G, Quaglio D, Balducci S, Berardozzi S Molecules. 2020; 25(2).

PMID: 31963860 PMC: 7024544. DOI: 10.3390/molecules25020414.

References

Martin S, Chen K, Eary C . An enantioselective total synthesis of (+)-geissoschizine. Org Lett. 2000; 1(1):79-81. DOI: 10.1021/ol990554a. View

Gremmen , Willemse , Wanner , Koomen . Enantiopure Tetrahydro-beta-carbolines via Pictet-Spengler Reactions with N-Sulfinyl Tryptamines. Org Lett. 2000; 2(13):1955-1958. DOI: 10.1021/ol006034t. View

Wang T, Cook J . General approach for the synthesis of sarpagine/ajmaline indole alkaloids. Stereospecific total synthesis of the sarpagine alkaloid (+)-vellosimine. Org Lett. 2000; 2(14):2057-9. DOI: 10.1021/ol000095+. View

Cox E, Hamaker L, Li J, Yu P, Czerwinski K, Deng L . Enantiospecific Formation of Trans 1,3-Disubstituted Tetrahydro-beta-carbolines by the Pictet-Spengler Reaction and Conversion of Cis Diastereomers into Their Trans Counterparts by Scission of the C-1/N-2 Bond. J Org Chem. 1997; 62(1):44-61. DOI: 10.1021/jo951170a. View

Bi L, Zhao M, Wang C, Peng S, Winterfeldt E . Diasteroselective cyclizations with enantiopure malonaldehyde monocycloacetals. J Org Chem. 2002; 67(1):22-6. DOI: 10.1021/jo0057351. View

Liu X, Deschamp J, Cook J . Regiospecific, enantiospecific total synthesis of the alkoxy-substituted indole bases, 16-epi-N(a)-methylgardneral, 11-methoxyaffinisine, and 11-methoxymacroline as well as the indole alkaloids alstophylline and macralstonine. Org Lett. 2002; 4(20):3339-42. DOI: 10.1021/ol020101x. View

Deiters A, Chen K, Eary C, Martin S . Biomimetic entry to the sarpagan family of indole alkaloids: total synthesis of +-geissoschizine and +-N-methylvellosimine. J Am Chem Soc. 2003; 125(15):4541-50. DOI: 10.1021/ja0296024. View

Yu J, Wang T, Wearing X, Ma J, Cook J . Enantiospecific total synthesis of (-)-(E)16-epiaffinisine, (+)-(E)16-epinormacusine B, and (+)-dehydro-16-epiaffinisine as well as the stereocontrolled total synthesis of alkaloid G. J Org Chem. 2003; 68(15):5852-9. DOI: 10.1021/jo030116o. View

Horiguchi Y, Nakamura M, Saitoh T, Sano T . A synthesis of chiral 1,1,3-trisubstituted 1,2,3,4-tetrahydro-beta-carbolines by the Pictet-Spengler reaction of tryptophan and ketones: conversion of (1R,3S)-diastereomers into their (1S,3S)-counterparts by scission of the C(1)-N(2) bond. Chem Pharm Bull (Tokyo). 2003; 51(12):1368-73. DOI: 10.1248/cpb.51.1368. View

10.

Bailey P, Clingan P, Mills T, Price R, Pritchard R . Total synthesis of (-)-raumacline. Chem Commun (Camb). 2003; (22):2800-1. DOI: 10.1039/b310274b. View

11.

Yamashita T, Kawai N, Tokuyama H, Fukuyama T . Stereocontrolled total synthesis of (-)-eudistomin C. J Am Chem Soc. 2005; 127(43):15038-9. DOI: 10.1021/ja055832h. View

12.

Stork G, Tang P, Casey M, Goodman B, Toyota M . Regiospecific and stereoselective syntheses of (+/-)-reserpine and (-)-reserpine. J Am Chem Soc. 2005; 127(46):16255-62. DOI: 10.1021/ja055744x. View

13.

Han D, Forsterling F, Deschamps J, Parrish D, Liu X, Yin W . Conformational analysis of the cis- and trans-adducts of the Pictet - Spengler reaction. Evidence for the structural basis for the C(1) - N(2) scission process in the cis- to trans-isomerization. J Nat Prod. 2007; 70(1):75-82. DOI: 10.1021/np060391g. View

14.

Amat M, Santos M, Bassas O, Llor N, Escolano C, Gomez-Esque A . Straightforward methodology for the enantioselective synthesis of benzo[a]- and indolo[2,3-a]quinolizidines. J Org Chem. 2007; 72(14):5193-201. DOI: 10.1021/jo070539g. View

15.

Ma J, Yin W, Zhou H, Cook J . Total synthesis of the opioid agonistic indole alkaloid mitragynine and the first total syntheses of 9-methoxygeissoschizol and 9-methoxy-Nb-methylgeissoschizol. Org Lett. 2007; 9(18):3491-4. PMC: 2526544. DOI: 10.1021/ol071220l. View

16.

Noren-Muller A, Wilk W, Saxena K, Schwalbe H, Kaiser M, Waldmann H . Discovery of a new class of inhibitors of Mycobacterium tuberculosis protein tyrosine phosphatase B by biology-oriented synthesis. Angew Chem Int Ed Engl. 2008; 47(32):5973-7. DOI: 10.1002/anie.200801566. View

17.

Ma J, Yin W, Zhou H, Liao X, Cook J . General approach to the total synthesis of 9-methoxy-substituted indole alkaloids: synthesis of mitragynine, as well as 9-methoxygeissoschizol and 9-methoxy-N(b)-methylgeissoschizol. J Org Chem. 2008; 74(1):264-73. PMC: 2654583. DOI: 10.1021/jo801839t. View

18.

Franzen J, Fisher A . Asymmetric alkaloid synthesis: a one-pot organocatalytic reaction to quinolizidine derivatives. Angew Chem Int Ed Engl. 2008; 48(4):787-91. DOI: 10.1002/anie.200805130. View

19.

Kumpaty H, van Linn M, Kabir M, Forsterling F, Deschamps J, Cook J . Study of the cis to trans isomerization of 1-phenyl-2,3-disubstituted tetrahydro-beta-carbolines at C(1). Evidence for the carbocation-mediated mechanism. J Org Chem. 2009; 74(7):2771-9. PMC: 2758420. DOI: 10.1021/jo8028168. View

20.

Wu X, Dai X, Nie L, Fang H, Chen J, Ren Z . Organocatalyzed enantioselective one-pot three-component access to indoloquinolizidines by a Michael addition-Pictet-Spengler sequence. Chem Commun (Camb). 2010; 46(16):2733-5. DOI: 10.1039/c001512a. View