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. 2017 Dec 15;21(12):2068-2072.
doi: 10.1021/acs.oprd.7b00312. Epub 2017 Nov 8.

Process Safety Assessment of the Iron-Catalyzed Direct Olefin Diazidation for the Expedient Synthesis of Vicinal Primary Diamines

Hai-Tao Zhu  1 , Luca Arosio  2 , Roberto Villa  2 , Marino Nebuloni  2 , Hao Xu  1
Affiliations

Process Safety Assessment of the Iron-Catalyzed Direct Olefin Diazidation for the Expedient Synthesis of Vicinal Primary Diamines

Hai-Tao Zhu et al. Org Process Res Dev. .

Abstract

We report herein a process safety assessment of the iron-catalyzed direct olefin diazidation for the preparation of a broad range of synthetically valuable vicinal primary diamines. Differential scanning calorimetry analysis of the corresponding reagents, intermediates, and a list of representative diazide/diaminium salt products revealed that all of them are thermal stable at the reaction temperature. The drop weight test of the diazides suggested that they are moderately impact-sensitive. Guided by this assessment, an optimized olefin diazidation/diamination procedure has been developed which allows for the gram-scale diaminium salt synthesis without purification of the diazide intermediate.

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Conflict of interest statement

Notes The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Representative vicinal diazides obtained from the iron-catalyzed olefin diazidation.
Figure 2
Figure 2
Differential scanning calorimetry (DSC) analysis of the reagents, products, and intermediates involved in the iron-catalyzed olefin diazidation/diamination.
Figure 3
Figure 3
Functionalized vicinal diazides analyzed by DSC.
Figure 4
Figure 4
(a) Dewar test of a “blank reaction”; (b) DSC analysis of the mixture from a runaway reaction in the absence of substrates and ligands.
Scheme 1
Scheme 1
Iron-Catalyzed Direct Olefin Diazidation for Vicinal Primary Diamine Synthesis
Scheme 2
Scheme 2
Iron-Catalyzed Procedure for Expedient Synthesis of trans-Indene Diaminium Salt
Scheme 3
Scheme 3
Mechanistic Analysis of the Iron-Catalyzed Olefin Diazidation
Scheme 4
Scheme 4
Iron-Catalyzed Gram-Scale Indene Diazidation/ Diamination Sequence that Excludes Chromatography Purification
See this image and copyright information in PMC

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