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Strategy for employing unstabilized nucleophiles in palladium-catalyzed asymmetric allylic alkylations.
J Am Chem Soc. 2008 Oct 29; 130(43):14092-3.JA

Abstract

We report a strategy for the employment of highly unstabilized anions in palladium-catalyzed asymmetric allylic alkylations (AAA). The "hard" 2-methylpyridyl nucleophiles studied are first reacted in situ with BF3.OEt2; subsequent deprotonation of the resulting complexes with LiHMDS affords "soft" anions that are competent nucleophiles in AAA reactions. The reaction is selective for the 2-position of methylpyridines and tolerates bulky aryl and alkyl substitution at the 3-, 4-, and 5-positions. Investigations into the reaction mechanism demonstrate that the configuration of the allylic stereocenter is retained, consistent with the canonical outer sphere mechanism invoked for palladium-catalyzed allylic substitution processes of stabilized anions.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Trost BM
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
Thaisrivongs DA
No affiliation info available

MeSH

AlkylationAllyl CompoundsCatalysisLigandsMolecular StructureOrganometallic CompoundsPalladiumPyridinesStereoisomerism

Pub Type(s)

Journal Article

Language

eng

PubMed ID

18826305

Citation

Trost, Barry M., and David A. Thaisrivongs. "Strategy for Employing Unstabilized Nucleophiles in Palladium-catalyzed Asymmetric Allylic Alkylations." Journal of the American Chemical Society, vol. 130, no. 43, 2008, pp. 14092-3.
Trost BM, Thaisrivongs DA. Strategy for employing unstabilized nucleophiles in palladium-catalyzed asymmetric allylic alkylations. J Am Chem Soc. 2008;130(43):14092-3.
Trost, B. M., & Thaisrivongs, D. A. (2008). Strategy for employing unstabilized nucleophiles in palladium-catalyzed asymmetric allylic alkylations. Journal of the American Chemical Society, 130(43), 14092-3. https://doi.org/10.1021/ja806781u
Trost BM, Thaisrivongs DA. Strategy for Employing Unstabilized Nucleophiles in Palladium-catalyzed Asymmetric Allylic Alkylations. J Am Chem Soc. 2008 Oct 29;130(43):14092-3. PubMed PMID: 18826305.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Strategy for employing unstabilized nucleophiles in palladium-catalyzed asymmetric allylic alkylations. AU - Trost,Barry M, AU - Thaisrivongs,David A, Y1 - 2008/10/01/ PY - 2008/10/2/pubmed PY - 2009/1/29/medline PY - 2008/10/2/entrez SP - 14092 EP - 3 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 130 IS - 43 N2 - We report a strategy for the employment of highly unstabilized anions in palladium-catalyzed asymmetric allylic alkylations (AAA). The "hard" 2-methylpyridyl nucleophiles studied are first reacted in situ with BF3.OEt2; subsequent deprotonation of the resulting complexes with LiHMDS affords "soft" anions that are competent nucleophiles in AAA reactions. The reaction is selective for the 2-position of methylpyridines and tolerates bulky aryl and alkyl substitution at the 3-, 4-, and 5-positions. Investigations into the reaction mechanism demonstrate that the configuration of the allylic stereocenter is retained, consistent with the canonical outer sphere mechanism invoked for palladium-catalyzed allylic substitution processes of stabilized anions. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/18826305/Strategy_for_employing_unstabilized_nucleophiles_in_palladium_catalyzed_asymmetric_allylic_alkylations_ L2 - https://doi.org/10.1021/ja806781u DB - PRIME DP - Unbound Medicine ER -