Directed beta-c(SP3)-h iodination and arylation of ketones

An iodination, oxime-based technology, applied in the field of directional β-C(sp3)-H iodination and arylation of ketones, which can solve incompatibility, substrate range and transformation limitations, interference with coupling agents and catalysts, etc. question

Active Publication Date: 2020-05-29
THE SCRIPPS RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

6 However, since free transient directing groups often interfere with coupling agents and catalysts, this strategy is incompatible with many synthetically desirable transformations
β-C(sp 3 )-H functionalization of ketones using covalent or transient directing groups compared to β-C(sp 3 )-H functionalization is very limited in both substrate scope and transformation

Method used

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  • Directed beta-c(SP3)-h iodination and arylation of ketones
  • Directed beta-c(SP3)-h iodination and arylation of ketones
  • Directed beta-c(SP3)-h iodination and arylation of ketones

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Experimental program
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Embodiment

[0068] General information

[0069] Ketones were obtained from commercial sources or synthesized according to literature procedures and used to prepare the corresponding substrates. Aminooxyacetic acid hemihydrochloride was obtained from Combi-Blocks. I 2 Obtained from TCI. PhI(OAc) 2 Obtained from Sigma-Aldrich. Solvents were obtained from Sigma-Aldrich, Alfa-Aesar and Acros and were used without further purification. Analytical thin layer chromatography was performed on 0.25 mm silica gel 60-F254. Visualization was performed using UV light and Vogel's permanganate. Recorded on Bruker AMX-400 instrument (400MHz) or Bruker DRX-600 instrument (600MHz) 1 H NMR. Chemical shifts are expressed in parts per million (ppm) relative to 0.0 ppm of tetramethylsilane. The following abbreviations (or combinations thereof) are used to explain multiplicity: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, br=broad. The coupling constant J is expressed in Hertz units (Hz). ...

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Abstract

This invention discloses the first example of palladium(II)-catalyzed beta-C(sp3)-H iodination or arylation of a wide range of ketones by using a commercially available amino-oxy-acetic acid auxiliary. This L, X-type directing group overcomes the limitation of the transient directing group approach for [beta]C(sp3)-H functionalization of ketones. Practical advantages of this method include simpleinstallation of the auxiliary without chromatography, exceptional tolerance of alpha-functional groups, double bonds and triple bonds and rapid access to diverse sterically hindered quaternary centers.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS [0002] This application claims priority to US Provisional Application Serial No. 62 / 546,166, filed August 16, 2017, the disclosure of which is incorporated herein by reference in its entirety. [0003] Statement of Government Support [0004] This invention was made with government support under Grant No. GM084019 awarded by the National Institutes of General Medical Sciences. The government has certain rights in this invention. Background technique [0005] Ketones are ubiquitous in organic chemistry, where they are used as valuable bulk chemicals, synthetic building blocks, and natural products. Although the reactivity of α-acidic C-H bonds has been extensively studied in asymmetric enol chemistry, 1 but inert β-C(sp 3 Direct functionalization of )-H bonds can further extend the synthetic utility of ketones by providing new synthetic cleavage groups. Although since the seminal work of Shaw, Sutherland, Baldwin et al., sto...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/093C07C49/16C07C249/08C07C251/34
CPCC07C249/04C07C249/12C07C253/30C07F7/1892C07C2601/14C07C2602/42C07C45/42C07C251/60C07C255/64C07C49/233B01J31/2226B01J2531/0219B01J2531/824
Inventor 余金权朱如意
Owner THE SCRIPPS RES INST
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