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. 2017 Dec 13;139(49):17787-17790.
doi: 10.1021/jacs.7b11663. Epub 2017 Dec 5.

Palladium-Catalyzed Dearomative syn-1,4-Carboamination

Mikiko Okumura  1 , Alexander S Shved  1 , David Sarlah  1
Affiliations

Palladium-Catalyzed Dearomative syn-1,4-Carboamination

Mikiko Okumura et al. J Am Chem Soc. .

Abstract

A dearomative 1,4-carboamination of arenes has been achieved using arenophile cycloaddition and subsequent palladium-catalyzed substitution with nonstabilized lithium enolates. This protocol delivers products with exclusive syn-1,4-selectivity and can be also conducted in an asymmetric fashion. The method allows rapid dearomative difunctionalization of simple aromatic compounds into functional small molecules amenable to further diversification.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Derivatization of product 16. Reagents and conditions: (a) Pd/C (cat.), H2, 60%; (b) (i) Rh/Al2O3 (cat.), H2, 93%; (ii) tBuOCl, AcOH, 79%; (c) (i) OsO4 (cat.), NMO, 87%; (ii) NaOCl, 40%; (d) (i) Rh/Al2O3 (cat.), H2, 93%; (ii) glycol, TsOH, 85%; (e) (i) α-bromoacetophenone, NaH, 78%; (ii) KOH, 97%; (f) NaOCl, 53%; (g) tBuOCl, 77%, 20:1 dr.
Scheme 1
Scheme 1
Dearomative Amino Functionalizations
See this image and copyright information in PMC

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