通过铱催化的烯丙基烷基化反应实现非环 α-季碳羧酸衍生物的对映选择性合成。
Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation.
机构信息
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101-20, Pasadena, CA, 91125, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Sep 11;56(38):11545-11548. doi: 10.1002/anie.201707015. Epub 2017 Aug 9.
Abstract
The first highly enantioselective iridium-catalyzed allylic alkylation that provides access to products bearing an allylic all-carbon quaternary stereogenic center has been developed. The reaction utilizes a masked acyl cyanide (MAC) reagent, which enables the one-pot preparation of α-quaternary carboxylic acids, esters, and amides with a high degree of enantioselectivity. The utility of these products is further explored through a series of diverse product transformations.
摘要
首次发展了一种高对映选择性的铱催化烯丙基烷基化反应，可获得具有烯丙基全碳季立体中心的产物。该反应利用了掩蔽的酰基氰化物（MAC）试剂，可实现α-季碳羧酸、酯和酰胺的一锅法制备，具有高度的对映选择性。通过一系列不同的产物转化进一步探索了这些产物的用途。
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本文引用的文献
1
The Catalytic Enantioselective Construction of Molecules with Quaternary Carbon Stereocenters.
Angew Chem Int Ed Engl. 1998 Mar 2;37(4):388-401. doi: 10.1002/(SICI)1521-3773(19980302)37:4<388::AID-ANIE388>3.0.CO;2-V.
2
Iridium-Catalyzed Diastereo-, Enantio-, and Regioselective Allylic Alkylation with Prochiral Enolates.
ACS Catal. 2016 Sep 2;6(9):6207-6213. doi: 10.1021/acscatal.6b01886. Epub 2016 Aug 17.
3
Enantioselective Iridium-Catalyzed Allylic Alkylation Reactions of Masked Acyl Cyanide Equivalents.
Org Lett. 2017 Apr 7;19(7):1527-1529. doi: 10.1021/acs.orglett.7b00449. Epub 2017 Mar 14.
4
Study of Intermediates in Iridium-(Phosphoramidite,Olefin)-Catalyzed Enantioselective Allylic Substitution.
J Am Chem Soc. 2017 Mar 15;139(10):3603-3606. doi: 10.1021/jacs.6b12421. Epub 2017 Mar 7.
5
Synthesis of α-Quaternary Formimides and Aldehydes through Umpolung Asymmetric Copper Catalysis with Isocyanides.
J Am Chem Soc. 2017 Feb 15;139(6):2184-2187. doi: 10.1021/jacs.6b12881. Epub 2017 Feb 1.
6
Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis.
J Am Chem Soc. 2017 Jan 11;139(1):87-90. doi: 10.1021/jacs.6b11692. Epub 2016 Dec 22.
7
Iridium-Catalyzed Stereoselective Allylic Alkylation Reactions with Crotyl Chloride.
Angew Chem Int Ed Engl. 2016 Dec 23;55(52):16092-16095. doi: 10.1002/anie.201609960. Epub 2016 Nov 28.
8
Enantioselective Synthesis of Quaternary Stereocenters via Chromium Catalysis.
Org Lett. 2016 Oct 7;18(19):5094-5097. doi: 10.1021/acs.orglett.6b02540. Epub 2016 Sep 13.
9
Iridium-Catalyzed Regio- and Enantioselective Allylic Substitution of Trisubstituted Allylic Electrophiles.
Angew Chem Int Ed Engl. 2016 Sep 12;55(38):11651-5. doi: 10.1002/anie.201607053. Epub 2016 Aug 17.
10
Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement.
J Am Chem Soc. 2016 Apr 27;138(16):5234-7. doi: 10.1021/jacs.6b02153. Epub 2016 Apr 18.
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