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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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References

    1. For recent reviews, see: Pirnot MT, Wang YM, Buchwald SL. Angew Chem, Int Ed. 2016;55:48.Huang L, Arndt M, Gooßen K, Heydt H, Gooßen LJ. Chem Rev. 2015;115:2596.McDonald RI, Liu G, Stahl SS. Chem Rev. 2011;111:2981.Hesp KD, Stradiotto M. ChemCatChem. 2010;2:1192.Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem Rev. 2008;108:3795.Hong S, Marks TJ. Acc Chem Res. 2004;37:673.Müller TE, Beller M. Chem Rev. 1998;98:675.

    1. For recent reviews, see: Newhouse T, Baran PS, Hoffmann RW. Chem Soc Rev. 2009;38:3010.Burns NZ, Baran PS. Angew Chem, Int Ed. 2008;47:205.Wender PA, Verma VA, Paxton TJ, Pillow TH. Acc Chem Res. 2008;41:40.

    1. For recent examples, see: Gockel SN, Buchanan TL, Hull KL. J Am Chem Soc. 2018;140:58.Qian B, Chen S, Wang T, Zhang X, Bao H. J Am Chem Soc. 2017;139:13076.Liu Z, Wang Y, Wang Z, Zeng T, Liu P, Engle KM. J Am Chem Soc. 2017;139:11261.White DR, Hutt JT, Wolfe JP. J Am Chem Soc. 2015;137:11246.Piou T, Rovis T. Nature. 2015;527:86.Liwosz TW, Chemler SR. J Am Chem Soc. 2012;134:2020.

    1. For recent examples, see: Davis-Gilbert ZW, Yao LJ, Tonks IA. J Am Chem Soc. 2016;138:14570.Kajita Y, Matsubara S, Kurahashi T. J Am Chem Soc. 2008;130:6058.Fürstner A, Davies PW. J Am Chem Soc. 2005;127:15024.Shimada T, Nakamura I, Yamamoto Y. J Am Chem Soc. 2004;126:10546.Ruck RT, Zuckerman RL, Krska SW, Bergman RG. Angew Chem, Int Ed. 2004;43:5372.

    1. For recent examples, see: Chen SS, Wu MS, Han ZY. Angew Chem, Int Ed. 2017;56:6641.Liu Y, Xie Y, Wang H, Huang H. J Am Chem Soc. 2016;138:4314.Houlden CE, Bailey CD, Ford JG, Gagné MR, Lloyd-Jones GC, Booker-Milburn KI. J Am Chem Soc. 2008;130:10066.

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