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Asymmetric [3+2] Annulation Approach to 3-Pyrrolines: Concise Total Syntheses of (-)-Supinidine, (-)-Isoretronecanol, and (+)-Elacomine.
Angew Chem Int Ed Engl. 2015 Nov 09; 54(46):13706-10.AC

Abstract

An asymmetric [3+2] annulation reaction to form 3-pyrroline products is reported. Upon treatment with lithium diisopropylamide, readily available ethyl 4-bromocrotonate is deprotonated and trapped with Ellman imines selectively at the α-position to yield enantiopure 3-pyrroline products. This new method is compatible with aryl, alkyl, and vinyl imines. The efficacy of the method is showcased by short asymmetric total syntheses of (-)-supinidine, (-)-isoretronecanol, and (+)-elacomine. This novel annulation approach also works for an aldehyde, thus providing access to a 2,5-dihydrofuran product in a single step from simple precursors. By modifying the structure of the carbanion nucleophile, an asymmetric vinylogous aza-Darzens reaction can be realized.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Chogii I
Department of Chemistry and Biochemistry, University of Arizona, 1306 E. University Blvd., Tucson AZ 85721 (USA) http://www.cbc.arizona.edu/njardarson/group.
Njardarson JT
Department of Chemistry and Biochemistry, University of Arizona, 1306 E. University Blvd., Tucson AZ 85721 (USA) http://www.cbc.arizona.edu/njardarson/group. njardars@email.arizona.edu.

MeSH

CyclizationIndolesMolecular StructurePyrrolesPyrrolizidine AlkaloidsSpiro CompoundsStereoisomerism

Pub Type(s)

Journal Article
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

26447827

Citation

Chogii, Isaac, and Jon T. Njardarson. "Asymmetric [3+2] Annulation Approach to 3-Pyrrolines: Concise Total Syntheses of (-)-Supinidine, (-)-Isoretronecanol, and (+)-Elacomine." Angewandte Chemie (International Ed. in English), vol. 54, no. 46, 2015, pp. 13706-10.
Chogii I, Njardarson JT. Asymmetric [3+2] Annulation Approach to 3-Pyrrolines: Concise Total Syntheses of (-)-Supinidine, (-)-Isoretronecanol, and (+)-Elacomine. Angew Chem Int Ed Engl. 2015;54(46):13706-10.
Chogii, I., & Njardarson, J. T. (2015). Asymmetric [3+2] Annulation Approach to 3-Pyrrolines: Concise Total Syntheses of (-)-Supinidine, (-)-Isoretronecanol, and (+)-Elacomine. Angewandte Chemie (International Ed. in English), 54(46), 13706-10. https://doi.org/10.1002/anie.201506559
Chogii I, Njardarson JT. Asymmetric [3+2] Annulation Approach to 3-Pyrrolines: Concise Total Syntheses of (-)-Supinidine, (-)-Isoretronecanol, and (+)-Elacomine. Angew Chem Int Ed Engl. 2015 Nov 9;54(46):13706-10. PubMed PMID: 26447827.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Asymmetric [3+2] Annulation Approach to 3-Pyrrolines: Concise Total Syntheses of (-)-Supinidine, (-)-Isoretronecanol, and (+)-Elacomine. AU - Chogii,Isaac, AU - Njardarson,Jon T, Y1 - 2015/10/08/ PY - 2015/07/15/received PY - 2015/09/12/revised PY - 2015/10/9/entrez PY - 2015/10/9/pubmed PY - 2016/8/16/medline KW - annulation KW - heterocycles KW - reaction mechanisms KW - synthetic methods KW - total synthesis SP - 13706 EP - 10 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 54 IS - 46 N2 - An asymmetric [3+2] annulation reaction to form 3-pyrroline products is reported. Upon treatment with lithium diisopropylamide, readily available ethyl 4-bromocrotonate is deprotonated and trapped with Ellman imines selectively at the α-position to yield enantiopure 3-pyrroline products. This new method is compatible with aryl, alkyl, and vinyl imines. The efficacy of the method is showcased by short asymmetric total syntheses of (-)-supinidine, (-)-isoretronecanol, and (+)-elacomine. This novel annulation approach also works for an aldehyde, thus providing access to a 2,5-dihydrofuran product in a single step from simple precursors. By modifying the structure of the carbanion nucleophile, an asymmetric vinylogous aza-Darzens reaction can be realized. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/26447827/Asymmetric_[3+2]_Annulation_Approach_to_3_Pyrrolines:_Concise_Total_Syntheses_of_____Supinidine_____Isoretronecanol_and__+__Elacomine_ DB - PRIME DP - Unbound Medicine ER -