Aminochlorination of Alkenes with CFBSA

Abstract

A novel catalyst‐free aminochlorination of alkenes was developed by the direct addition of alkenes to N‐chloro‐N‐fluorobenzenesulfonamide (CFBSA). The reaction produces 2‐chloro‐3‐fluoramino and 3‐chloro‐2‐fluoroamino adducts in 1,2‐dichloroethane under reflux and dichloromethane at room temperature, respectively, in a regioselective manner. The electronic and steric effects of the fluorine atom of CFBSA have proven to be crucial for the reactivity and regioselectivity. A variety of transformations have been achieved to form 2‐chloroenamines, chloroamines, aziridines and N‐phenylbenzenesulfonamides under different conditions. Notably, the N–F bond in the adducts formed could be a useful handle for further transformations to useful compounds in organic synthesis.

Enantioselective Catalytic Synthesis of α-Halogenated α-Aryl-β2,2-amino Acid Derivatives

“…The synthesis of chiral α-Cl-β 2,2 -AA has been very sparingly reported so far, ,, and to the best of our knowledge, a reliable asymmetric catalysis approach to access (masked) α-Cl-β 2,2 -AA derivatives is yet missing. Considering the general value of enantioenriched α-Cl-carbonyl compounds to serve as building blocks for further manipulations (i.e., stereospecific S N 2-type reactions), − we now became interested in developing a protocol for the asymmetric electrophilic α-chlorination , of isoxazolidin-5-ones 1 using the established chiral ammonium salt ion pairing catalysts A – C (Figure ).…”

Chlorination of Anilide by Pd(OAc)2/N-Chloro-N-fluorobenzene- sulfonylamide

“…Therefore, CFBSA is equipped with the property of oxidant. Several studies show that it is also an efficient chlorinating reagent, such as aminochlorination of alkenes, [21,23] chlorination of carbonyl and nitrogen-containing aromatic heterocyclic compounds. [13] Particularly, aniline could be chlorinated to afford 2,4,6-trichloroaniline with CFBSA as chlorinating reagent.…”

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

“…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 ), TsNCl 2 (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-NsNCl 2 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.…”