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配体控制的区域发散性钯催化脱羧烯丙基化反应合成α,α-二氟酮

Ligand-controlled regiodivergent palladium-catalyzed decarboxylative allylation reaction to access α,α-difluoroketones.

作者信息

Yang Ming-Hsiu, Orsi Douglas L, Altman Ryan A

机构信息

Department of Medicinal Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, KS 66045 (USA).

出版信息

Angew Chem Int Ed Engl. 2015 Feb 16;54(8):2361-5. doi: 10.1002/anie.201410039. Epub 2015 Jan 7.

Abstract

α,α-Difluoroketones possess unique physicochemical properties that are useful for developing therapeutics and probes for chemical biology. To access the α-allyl-α,α-difluoroketone substructure, complementary palladium-catalyzed decarboxylative allylation reactions were developed to provide linear and branched α-allyl-α,α-difluoroketones. For these orthogonal processes, the fluorination pattern of the substrate enabled the ligands to dictate the regioselectivity of the transformations.

摘要

α,α-二氟酮具有独特的物理化学性质,这对于开发治疗药物和化学生物学探针很有用。为了获得α-烯丙基-α,α-二氟酮亚结构,人们开发了互补的钯催化脱羧烯丙基化反应,以提供直链和支链的α-烯丙基-α,α-二氟酮。对于这些正交反应,底物的氟化模式使配体能够决定转化反应的区域选择性。

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本文引用的文献

1
New Ligands for Regio- and Enantiocontrol in Pd-Catalyzed Allylic Alkylations.
Angew Chem Int Ed Engl. 1998 Feb 16;37(3):323-325. doi: 10.1002/(SICI)1521-3773(19980216)37:3<323::AID-ANIE323>3.0.CO;2-T.
2
Copper-Catalyzed Decarboxylative Trifluoromethylation of Propargyl Bromodifluoroacetates.
Synthesis (Stuttg). 2014 Jul 15;46(14):1938-1946. doi: 10.1055/s-0033-1339128.
3
Metal-free trifluoromethylation of aromatic and heteroaromatic aldehydes and ketones.
J Org Chem. 2014 Aug 1;79(15):7122-31. doi: 10.1021/jo501289v. Epub 2014 Jul 15.
4
Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.
Org Lett. 2013 Nov 1;15(21):5578-81. doi: 10.1021/ol402780k. Epub 2013 Oct 11.
6
Evaluation of difluoromethyl ketones as agonists of the γ-aminobutyric acid type B (GABAB) receptor.
J Med Chem. 2013 Mar 28;56(6):2456-65. doi: 10.1021/jm301805e. Epub 2013 Mar 6.
7
Achieving control over the branched/linear selectivity in palladium-catalyzed allylic amination.
J Org Chem. 2013 Feb 15;78(4):1559-75. doi: 10.1021/jo3025253. Epub 2013 Feb 6.
9
Dialkylbiaryl Phosphines in Pd-Catalyzed Amination: A User's Guide.
Chem Sci. 2011;2(1):27-50. doi: 10.1039/C0SC00331J.

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