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. 2018 Apr 4;140(13):4503-4507.
doi: 10.1021/jacs.8b01726. Epub 2018 Mar 23.

Nickel-Catalyzed Dearomative trans-1,2-Carboamination

Lucas W Hernandez  1 , Ulrich Klöckner  1 , Jola Pospech  1 , Lilian Hauss  1 , David Sarlah  1
Affiliations

Nickel-Catalyzed Dearomative trans-1,2-Carboamination

Lucas W Hernandez et al. J Am Chem Soc. .

Abstract

We describe the development of an arenophile-mediated, nickel-catalyzed dearomative trans-1,2-carboamination protocol. A range of readily available aromatic compounds was converted to the corresponding dienes using Grignard reagents as nucleophiles. This strategy provided products with exclusive trans-selectivity and high enantioselectivity was observed in case of benzene and naphthalene. The utility of this methodology was showcased by controlled and stereoselective preparation of small, functionalized molecules.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Derivatization of benzene- and naphthalene-derived products 2a and 2o. Reagents and conditions: (a) (i) α-bromoacetophenone, K2CO3, 94%; (ii) H2, Pt(S)/C (cat.), 91%; then KOH, 73%; (b) (i) α-bromoacetophenone, K2CO3, 94%; (ii) TPP, O2, visible-light, 65%; (iii) thiourea, then KOH, 73%; (c) (i) α-bromoacetophenone, K2CO3, 94% (ii) MTAD, 68%; (iii) KOH, then BzCl, then SmI2, 67%; (d) (i) α-bromoacetophenone, K2CO3, 91%; (ii) H2, Pt(S)/C (cat.), 92%; (iii) KOH, 82%; (e) (i) H2, Pd/C (cat.), 95%; (ii) NaOCl, 53%; (f) (i) H2, Pd/C (cat.), 95%; (ii) Li, NH3, 69%.
Scheme 1
Scheme 1
Dearomative Carboaminations
See this image and copyright information in PMC

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