Hypervalent Iodine (III) Catalyzed Regio- and Diastereoselective Aminochlorination of Tailored Electron Deficient Olefins via GAP Chemistry

Anis Ur Rahman,Peng Zhou,Nighat Zarshad,Guigen Li,Asad Ali,Weitao Yang

doi:10.3389/fchem.2020.00523

Abstract

Herein, we report a protocol for highly efficient hypervalent iodine (III) mediated, group-assisted purification (GAP) method for the regioselectivities and stereoselective aminochlorination of electron-deficient olefins. A series of vicinal chloramines with multifunctionalities were acquired in moderate to excellent yields (45–94%), by merely mixing the GAP auxiliary-anchored substrates with dichloramine T and tosylamide as chlorine/nitrogen sources and iodobenzene diacetate as a catalyst. The vicinal chloramines were obtained without any column chromatographic purification and recrystallization simply by washing the reaction mixture with a minimum amount of common inexpensive solvents and thus avoiding wastage of silica, solvents, time, and labor. The GAP auxiliary is recyclable and reusable. This strategy is easy to handle, cost-effective, greener, sustainable, environmentally benign, and mostly suitable for the syntheses of vicinal haloamines from various electron-deficient alkenes.

Highlights

Aminohalogenation of olefins is one of the most effective approaches to produce functional α,β-haloamines
The aforementioned synthesis usually involves the use of traditional methods of purification such as column chromatography and recrystallization
We initiated the study by investigating group-assisted purification (GAP) auxiliaries and their potential application in GAP chemistry

Summary

Introduction

Aminohalogenation of olefins is one of the most effective approaches to produce functional α,β-haloamines. Several research groups have made great contributions in developing both intermolecular and intramolecular aminohalogenation (Minakata et al, 2006; Li et al, 2007; Michael et al, 2008; Chen et al, 2010; Denmark et al, 2012; Yin et al, 2012; Chemler and Bovino, 2013; Song et al, 2013, 2016; Martínez and Muñiz, 2014; Broggini et al, 2015; Qin et al, 2015; Zhu et al, 2015; Legnani et al, 2018; Cai et al, 2019), in which a series of halogen/nitrogen sources, such as CFBSA (Pu et al, 2016), NCS/MeCN (Tay et al, 2013), NCP (Zhu et al, 2018), NFSI/TMSCl (Arteaga et al, 2018), TsNCl2 (Han et al, 2007; Wu and Wang, 2008; Wei et al, 2009), TsNHCl (Cai et al, 2011), TsNNaCl (Martínez and Muñiz, 2014), 2-NsNNaCl (Li et al, 2001), or the combination of 2-NsNCl2 and 2-NsNHNa (Liu et al, 2006), and so on, were employed for many types of alkene substrates Most of these aminohalogenation systems take advantage of metals or organic catalysts to give good yields and excellent regioselectivities and diastereoselectivities. In this report, we would like to present the design of new group-assisted purification (GAP) group-attached olefin substrates and their potentials for aminochlorination enabling ste minimized, greener GAP workup, and purification

Methods

Results

Conclusion