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. 2022 Aug 1;61(31):e202205440.
doi: 10.1002/anie.202205440. Epub 2022 Jun 13.

Preparation of Functionalized Amides Using Dicarbamoylzincs

Dimitrije Djukanovic  1 , Maximilian A Ganiek  2 , Kohei Nishi  3   4 , Konstantin Karaghiosoff  1 , Kazushi Mashima  3   4 , Paul Knochel  1
Affiliations

Preparation of Functionalized Amides Using Dicarbamoylzincs

Dimitrije Djukanovic et al. Angew Chem Int Ed Engl. .

Abstract

We report a new convenient preparation of dicarbamoylzincs of type (R1 R2 NCO)2 Zn by the treatment of ZnCl2 and formamides R1 R2 NCHO with LiTMP in THF (15 °C, 15 min) or by the reaction of formamides R1 R2 NCHO with TMP2 Zn (25 °C, 16 h). This second method tolerates sensitive groups such as an ester, ketone or nitro function. Reaction of these dicarbamoylzincs with allylic, benzylic, aryl, alkenyl bromides, acid chlorides, aldehydes or enones provided various polyfunctional amides in 47-97 % yields. 13 C NMR characterization of these new carbamoylzinc derivatives is reported.

Keywords: Amides; Carbamoyl; Lithium; Metalation; Zinc.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Preparations of carbamoylmetal reagents.
Scheme 2
Scheme 2
Allylation of dicarbamoylzincs of type 6 with allylic and propargylic bromides providing polyfunctional amides of type 8. The indicated yields refer to analytically pure isolated product.
Scheme 3
Scheme 3
Allylation of dicarbamoylzincs of type 6 with allylic bromides providing polyfunctional amides of type 8. The indicated yields refer to analytically pure isolated product.
Scheme 4
Scheme 4
Cu‐catalyzed benzylation of dicarbamoylzincs 6 with benzylic bromides. The indicated yields refer to analytically pure isolated product.
Scheme 5
Scheme 5
Mg‐mediated hydroxyalkylation of dicarbamoylzincs 6 with aldehydes. The indicated yields refer to analytically pure isolated product.
Scheme 6
Scheme 6
Acylation of dicarbamoylzincs 6 with acid chlorides. The indicated yields refer to analytically pure isolated product.
Scheme 7
Scheme 7
Cu‐mediated 1,4‐addition of 6 a to 2‐cyclohexen‐1‐one in the presence of BF3⋅OEt2. The indicated yields refer to analytically pure isolated product.
Scheme 8
Scheme 8
Pd‐ and Cu‐dual catalyzed cross‐couplings of dicarbamoylzincs 6 with aryl and alkenyl bromides. The indicated yields refer to analytically pure isolated product. [a] Metalation performed with TMP2Zn⋅2 MgCl2⋅2 LiCl. [b] Reaction performed from alkenyl iodides using CuCN⋅2 LiCl (1.0 equiv) without [Pd] catalyst.
Figure 1
Figure 1
13C NMR spectra of dicarbamoylzinc 6 a and lithium tricarbamoylzincate 14 a generated via different methods.
See this image and copyright information in PMC

References

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