Enantioselective Synthesis of (+)-isolysergol Via Ring-closing Metathesis

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2010 May 14

PMID 20462232

Citations 9

Authors

Jason A Deck

Stephen F Martin

Affiliations

Soon will be listed here.

Abstract

The first enantioselective synthesis of (+)-isolysergol was completed in 12 steps from commercially available materials by a novel approach that features a late stage microwave-mediated, diastereomeric ring-closing metathesis catalyzed by a chiral molybdenum catalyst to simultaneously form the D ring and set the stereocenter at C(8).

Citing Articles

Palladium-Catalyzed Aminocyclization-Coupling Cascades: Preparation of Dehydrotryptophan Derivatives and Computational Study.

Vaz B, Martinez C, Cruz F, Denis J, de Lera A, Aurrecoechea J J Org Chem. 2021; 86(13):8766-8785.

PMID: 34125552 PMC: 8929666. DOI: 10.1021/acs.joc.1c00636.

Total Synthesis of (±)-Quinagolide: A Potent D Receptor Agonist for the Treatment of Hyperprolactinemia.

Chavan S, Kadam A, Kawale S ACS Omega. 2019; 4(5):8231-8238.

PMID: 31459911 PMC: 6648496. DOI: 10.1021/acsomega.9b00903.

Natural Products and Their Mimics as Targets of Opportunity for Discovery.

Martin S J Org Chem. 2017; 82(20):10757-10794.

PMID: 28738152 PMC: 5653958. DOI: 10.1021/acs.joc.7b01368.

Applications of Ring Closing Metathesis. Total Synthesis of (±)-Pseudotabersonine.

Cheng B, Sunderhaus J, Martin S Tetrahedron. 2015; 71(39):7323-7331.

PMID: 26300565 PMC: 4542060. DOI: 10.1016/j.tet.2015.04.082.

Total synthesis of dihydrolysergic acid and dihydrolysergol: development of a divergent synthetic strategy applicable to rapid assembly of D-ring analogs.

Lee K, Poudel Y, Glinkerman C, Boger D Tetrahedron. 2015; 71(35):5897-5905.

PMID: 26273113 PMC: 4528678. DOI: 10.1016/j.tet.2015.05.093.

References

Neipp C, Martin S . Synthesis of bridged azabicyclic structures via ring-closing olefin metathesis. J Org Chem. 2003; 68(23):8867-78. DOI: 10.1021/jo0349936. View

Humphrey J, Liao Y, Ali A, Rein T, Wong Y, Chen H . Enantioselective total syntheses of manzamine a and related alkaloids. J Am Chem Soc. 2002; 124(29):8584-92. DOI: 10.1021/ja0202964. View

Schrock R, Hoveyda A . Molybdenum and tungsten imido alkylidene complexes as efficient olefin-metathesis catalysts. Angew Chem Int Ed Engl. 2003; 42(38):4592-633. DOI: 10.1002/anie.200300576. View

Inuki S, Oishi S, Fujii N, Ohno H . Total synthesis of (+/-)-lysergic acid, lysergol, and isolysergol by palladium-catalyzed domino cyclization of amino allenes bearing a bromoindolyl group. Org Lett. 2008; 10(22):5239-42. DOI: 10.1021/ol8022648. View

Moldvai I, Temesvari-Major E, Incze M, Szentirmay E, Gacs-Baitz E, Szantay C . Enantioefficient synthesis of alpha-ergocryptine: first direct synthesis of (+)-lysergic acid. J Org Chem. 2004; 69(18):5993-6000. DOI: 10.1021/jo049209b. View

Lin C, Blair G, Cassady J, Groger D, Maier W, Floss H . Biosynthesis of ergot alkaloids. Synthesis of 6-methyl-8-acetoxymethylene-9-ergolene and its incorporation into ergotoxine by Claviceps. J Org Chem. 1973; 38(12):2249-51. DOI: 10.1021/jo00952a035. View

Deiters A, Pettersson M, Martin S . General strategy for the syntheses of corynanthe, tacaman, and oxindole alkaloids. J Org Chem. 2006; 71(17):6547-61. DOI: 10.1021/jo061032t. View

Mukherjee J, Menge M . Progress and prospects of ergot alkaloid research. Adv Biochem Eng Biotechnol. 2000; 68:1-20. DOI: 10.1007/3-540-45564-7_1. View

Simila S, Martin S . Toward the total synthesis of FR901483: concise synthesis of the azatricyclic skeleton. J Org Chem. 2007; 72(14):5342-9. PMC: 2536713. DOI: 10.1021/jo070732a. View

10.

Andrade R, Martin S . Formal syntheses of (+/-)-pinnaic acid and (+/-)-halichlorine. Org Lett. 2005; 7(25):5733-5. PMC: 2536714. DOI: 10.1021/ol0525009. View

11.

Deiters A, Martin S . Synthesis of oxygen- and nitrogen-containing heterocycles by ring-closing metathesis. Chem Rev. 2004; 104(5):2199-238. DOI: 10.1021/cr0200872. View

12.

Washburn D, Heidebrecht Jr R, Martin S . Concise formal synthesis of (-)-peduncularine via ring-closing metathesis. Org Lett. 2003; 5(19):3523-5. DOI: 10.1021/ol0354066. View

13.

Hendrickson J, Wang J . A new synthesis of lysergic acid. Org Lett. 2004; 6(1):3-5. DOI: 10.1021/ol0354369. View

14.

Choong T, Thompson B, Shough H . Synthesis of 10alpha-methoxy-delta8,9-lysergaldehyde from elymoclavine. J Pharm Sci. 1977; 66(9):1340-1. DOI: 10.1002/jps.2600660937. View