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Enantioselective synthesis of α-quaternary Mannich adducts by palladium-catalyzed allylic alkylation: total synthesis of (+)-sibirinine.
J Am Chem Soc. 2015 Jan 28; 137(3):1040-3.JA

Abstract

A catalytic enantioselective method for the synthesis of α-quaternary Mannich-type products is reported. The two-step sequence of (1) Mannich reaction followed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effect access asymmetric Mannich-type products of "thermodynamic" enolates of substrates possessing additional enolizable positions and acidic protons. Palladium-catalyzed decarboxylative allylic alkylation enables the enantioselective synthesis of five-, six-, and seven-membered ketone, lactam, and other heterocyclic systems. The mild reaction conditions are notable given the acidic free N-H groups and high functional group tolerance in each of the substrates. The utility of this method is highlighted in the first total synthesis of (+)-sibirinine.

Authors+Show Affiliations

Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.No affiliation info availableNo affiliation info availableNo affiliation info available

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

25578104

Citation

Numajiri, Yoshitaka, et al. "Enantioselective Synthesis of Α-quaternary Mannich Adducts By Palladium-catalyzed Allylic Alkylation: Total Synthesis of (+)-sibirinine." Journal of the American Chemical Society, vol. 137, no. 3, 2015, pp. 1040-3.
Numajiri Y, Pritchett BP, Chiyoda K, et al. Enantioselective synthesis of α-quaternary Mannich adducts by palladium-catalyzed allylic alkylation: total synthesis of (+)-sibirinine. J Am Chem Soc. 2015;137(3):1040-3.
Numajiri, Y., Pritchett, B. P., Chiyoda, K., & Stoltz, B. M. (2015). Enantioselective synthesis of α-quaternary Mannich adducts by palladium-catalyzed allylic alkylation: total synthesis of (+)-sibirinine. Journal of the American Chemical Society, 137(3), 1040-3. https://doi.org/10.1021/ja512124c
Numajiri Y, et al. Enantioselective Synthesis of Α-quaternary Mannich Adducts By Palladium-catalyzed Allylic Alkylation: Total Synthesis of (+)-sibirinine. J Am Chem Soc. 2015 Jan 28;137(3):1040-3. PubMed PMID: 25578104.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Enantioselective synthesis of α-quaternary Mannich adducts by palladium-catalyzed allylic alkylation: total synthesis of (+)-sibirinine. AU - Numajiri,Yoshitaka, AU - Pritchett,Beau P, AU - Chiyoda,Koji, AU - Stoltz,Brian M, Y1 - 2015/01/20/ PY - 2015/1/13/entrez PY - 2015/1/13/pubmed PY - 2015/9/30/medline SP - 1040 EP - 3 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 137 IS - 3 N2 - A catalytic enantioselective method for the synthesis of α-quaternary Mannich-type products is reported. The two-step sequence of (1) Mannich reaction followed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effect access asymmetric Mannich-type products of "thermodynamic" enolates of substrates possessing additional enolizable positions and acidic protons. Palladium-catalyzed decarboxylative allylic alkylation enables the enantioselective synthesis of five-, six-, and seven-membered ketone, lactam, and other heterocyclic systems. The mild reaction conditions are notable given the acidic free N-H groups and high functional group tolerance in each of the substrates. The utility of this method is highlighted in the first total synthesis of (+)-sibirinine. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/25578104/Enantioselective_synthesis_of_α_quaternary_Mannich_adducts_by_palladium_catalyzed_allylic_alkylation:_total_synthesis_of__+__sibirinine_ L2 - https://doi.org/10.1021/ja512124c DB - PRIME DP - Unbound Medicine ER -