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A convergent Pd-catalyzed asymmetric allylic alkylation of dl- and meso-divinylethylene carbonate: enantioselective synthesis of (+)-australine hydrochloride and formal synthesis of isoaltholactone.
Chemistry. 2007; 13(34):9547-60.C

Abstract

The use of a mixture of dl- and meso-divinylethylene carbonate as an electrophile in palladium-catalyzed asymmetric allylic alkylation reactions is reported. From the diastereomeric mixture of meso and chiral racemic starting materials, a single product is obtained in high optical purity employing either oxygen or nitrogen nucleophiles. The resulting dienes have proven to be versatile synthetic intermediates as each carbon is functionalized for further transformation and differentiated by virtue of the reaction. A mechanism for this intriguing transformation is proposed and a concise enantioselective total synthesis of (+)-australine hydrochloride is reported as well as a formal synthesis of isoaltholactone.

Authors+Show Affiliations

Trost BM
Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA. bmtrost@stanford.edu
Aponick A
No affiliation info available
Stanzl BN
No affiliation info available

MeSH

Allyl CompoundsAminationCarbonatesCatalysisEthylenesFuransMolecular StructurePalladiumPhenolsPyronesPyrrolizidine AlkaloidsStereoisomerismVinyl Compounds

Pub Type(s)

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

Language

eng

PubMed ID

17847148

Citation

Trost, Barry M., et al. "A Convergent Pd-catalyzed Asymmetric Allylic Alkylation of Dl- and Meso-divinylethylene Carbonate: Enantioselective Synthesis of (+)-australine Hydrochloride and Formal Synthesis of Isoaltholactone." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 13, no. 34, 2007, pp. 9547-60.
Trost BM, Aponick A, Stanzl BN. A convergent Pd-catalyzed asymmetric allylic alkylation of dl- and meso-divinylethylene carbonate: enantioselective synthesis of (+)-australine hydrochloride and formal synthesis of isoaltholactone. Chemistry. 2007;13(34):9547-60.
Trost, B. M., Aponick, A., & Stanzl, B. N. (2007). A convergent Pd-catalyzed asymmetric allylic alkylation of dl- and meso-divinylethylene carbonate: enantioselective synthesis of (+)-australine hydrochloride and formal synthesis of isoaltholactone. Chemistry (Weinheim an Der Bergstrasse, Germany), 13(34), 9547-60.
Trost BM, Aponick A, Stanzl BN. A Convergent Pd-catalyzed Asymmetric Allylic Alkylation of Dl- and Meso-divinylethylene Carbonate: Enantioselective Synthesis of (+)-australine Hydrochloride and Formal Synthesis of Isoaltholactone. Chemistry. 2007;13(34):9547-60. PubMed PMID: 17847148.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A convergent Pd-catalyzed asymmetric allylic alkylation of dl- and meso-divinylethylene carbonate: enantioselective synthesis of (+)-australine hydrochloride and formal synthesis of isoaltholactone. AU - Trost,Barry M, AU - Aponick,Aaron, AU - Stanzl,Benjamin N, PY - 2007/9/12/pubmed PY - 2008/2/27/medline PY - 2007/9/12/entrez SP - 9547 EP - 60 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 13 IS - 34 N2 - The use of a mixture of dl- and meso-divinylethylene carbonate as an electrophile in palladium-catalyzed asymmetric allylic alkylation reactions is reported. From the diastereomeric mixture of meso and chiral racemic starting materials, a single product is obtained in high optical purity employing either oxygen or nitrogen nucleophiles. The resulting dienes have proven to be versatile synthetic intermediates as each carbon is functionalized for further transformation and differentiated by virtue of the reaction. A mechanism for this intriguing transformation is proposed and a concise enantioselective total synthesis of (+)-australine hydrochloride is reported as well as a formal synthesis of isoaltholactone. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/17847148/A_convergent_Pd_catalyzed_asymmetric_allylic_alkylation_of_dl__and_meso_divinylethylene_carbonate:_enantioselective_synthesis_of__+__australine_hydrochloride_and_formal_synthesis_of_isoaltholactone_ L2 - https://doi.org/10.1002/chem.200700832 DB - PRIME DP - Unbound Medicine ER -