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. 2019 Mar 1;21(5):1547-1550.
doi: 10.1021/acs.orglett.9b00427. Epub 2019 Feb 21.

Iron-Catalyzed Hydroamination and Hydroetherification of Unactivated Alkenes

Paul T Marcyk  1 , Silas P Cook  1
Affiliations

Iron-Catalyzed Hydroamination and Hydroetherification of Unactivated Alkenes

Paul T Marcyk et al. Org Lett. .

Abstract

The hydrofunctionalization of alkenes, explored for over 100 years, offers the potential for a direct, atom-economical approach to value-added products. While thermodynamically favored, the kinetic barrier to such processes necessitates the use of catalysts to control selectivity and reactivity. Modern variants typically rely on noble metals that require different ligands for each class of hydrofunctionalization, thereby limiting generality. This Letter describes a general iron-based system that catalyzes the hydroamination and hydroetherification of simple unactivated olefins.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
(a) Hydroamination, hydroetherification, and hydrothiolation require different conditions for each reaction. (b) This work offers a single catalyst for sulfonamides, alcohols, and a thiophenol.
Scheme 1.
Scheme 1.. Hydroam ination with Sulfonamide Nucleophiles
Reactions run at 0.5mmol scale.
Scheme 2.
Scheme 2.. Alkene Scope for Hydroam ination
Reactions run at 0.5 mmol scale, [a] Mixture of 2- and 3-substituted products, [b] FeCI3 only, [c] FeCI3 only, reaction run at r.t.
Scheme 3.
Scheme 3.. Hydroetherification and Hydrothiolation
Reactions run at 0.5 mmol scale, [a] Yield obtained by GC using dodecane internal standard.
Scheme 4.
Scheme 4.. Alkene Scope for Hydroetherification
PNP = 4-Nitrophenyl. Reactions run at 0.5 mmol scale, [a] Mixture of 2- and 3-substituted products. [b] FeCI3 only, [c] FeCk only, run at r.t. [d] 1 equiv alkene used.
See this image and copyright information in PMC

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