Dirhodium(II)-Catalyzed Synthesis of N-(Arylsulfonyl)hydrazines by N–H Amination of Aliphatic Amines

Abstract

This study reports the development of Rh(II)-catalyzed N–N bond-forming reaction of amino acid derivatives or aliphatic amines to provide hydrazine derivatives through the combined use of Rh₂(esp)₂ and [(3,4-dimethoxyphenyl)sulfonylimino]-2,4,6-trimethylphenyliodinane (3,4-(MeO)₂C₆H₃SO₂N=IMes). This is the first report of N–H amination of aliphatic amines with metal–nitrene species.

Key words

amine - hydrazine - N–N bond - Rh(II) catalyst - nitrene

Publication History

Received: 07 December 2021

Accepted after revision: 20 December 2021

Article published online:
13 January 2022

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It is reported that aminimides formed through the reactions of bicyclic aminals or (sulfon)amides and Rh(II)–nitrene underwent rearrangement to form formal C–N or S–N bond insertion products:
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We previously reported ortho C–H amination of tertiary aromatic amines with Rh(II)–nitrene and presumed that the regioselectivity was due to the interaction between amino group and nitrogen atom of Rh(II)-nitrene:
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An example of hydrazine formation from N-allylaniline is also reported in this study:
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• 13 N-Benzyl-1-aminocyclopropanecarboxylate provided a similar result to 1a. We choose 1a as the substrate because purification of the N–H amination product 3ad was easier than that obtained from the N-benzyl substrate.
• 14 In our previous work, the reaction at higher concentration (0.1 M) led to the formation of azo compounds by dimerization of primary aromatic amines, see ref. 12a.
• 15 Typical Experimental Procedure 3,4-(MeO)₂C₆H₃SO₂N=IMes (5d, 554 mg, 1.20 mmol) was added to a stirred mixture of 1a (233 mg, 1.00 mmol), Rh₂(esp)₂ (15.2 mg, 2.00·10^–2 mmol, 2 mol%), and MS 4 Å (powder, 400 mg) in CF₃C₆H₅ (40 mL) at 0 °C under Ar atmosphere. After stirring at room temperature for 1 h, the whole mixture was filtered through a pad of Celite, and the filtrate was concentrated in vacuo to furnish the crude product, which was purified by column chromatography (silica gel, 1:1 n-hexane/AcOEt) to give 3ad (364 mg, 81%) as orange oil. IR (KBr): ν = 3279, 2933, 1722, 1511, 1165, 1029 cm^–1. ¹H NMR (400 MHz, CD₃CN, 60 °C): δ = 0.90 (br d, 2 H, c-propane), 1.05 (t, J = 7.2 Hz, 3 H, CH₂CH ₃), 1.25 (br s, 2 H, c-propane), 2.21 (s, 3 H, ArCH₃), 3.66 (s, 3 H, OCH₃), 3.69 (s, 3 H, OCH₃), 3.90 (q, J = 7.2 Hz, 2 H, CH ₂CH₃), 4.41 (s, 2 H, ArCH₂), 6.60 (dd, J = 8.4, 2.6 Hz, 1 H, ArH), 6.62 (d, J = 2.6 Hz, 1 H, ArH), 6.77 (d, J = 8.4 Hz, 1 H, ArH), 7.02 (d, J = 8.0 Hz, 2 H, ArH), 7.09–7.11 (m, 3 H, NH and ArH). ¹³C NMR (100 MHz, CD₃CN, 60 °C): δ = 14.6 (CH₃), 20.1 (CH₂), 21.3 (CH₃), 43.6 (C), 54.8 (CH₂), 56.9 (CH₃), 57.2 (CH₃), 62.5 (CH₂), 109.9 (CH), 113.9 (CH), 116.8 (CH), 130.1 (CH), 130.5 (CH) 131.9 (C), 135.2 (C), 138.8 (C), 148.8 (C), 151.0 (C), 174.0 (C=O). HRMS (EI): m/z calcd for C₂₂H₂₈N₂O₆S [M]⁺: 448.1668; found: 448.1666.