A minireview of hydroamination catalysis: alkene and alkyne substrate selective, metal complex design

Abstract

Organic compounds that contain nitrogen are very important intermediates in pharmaceutical and chemical industry. Hydroamination is the reaction that can form C – N bond with high atom economy. The research progress in metals catalyzed hydroamination of alkenes and alkynes from the perspective of reaction mechanism is categorized and summarized.

Nickel/Brønsted Acid-Catalyzed Chemo- and Enantioselective Intermolecular Hydroamination of Conjugated Dienes

“…Therefore, organic chemists have made considerable efforts toward their synthesis during the last decade (Grogan, 2018, Li and Zhang, 2014, Nugent and El-Shazly, 2010, Patil et al., 2018, Robak et al., 2010). Among them, asymmetric hydroamination of unsaturated C-C bonds serves as an efficient and powerful tool in organic synthesis, particularly hydroamination using free amines (Aillaud et al., 2007, Clement and Jerome, 2017, Dondoni, 2015, Hannedouche and Schulz, 2013, Hannedouche and Schulz, 2018, Hii, 2006, Huang et al., 2015, Huo et al., 2019, Jerome, 2018, Müller et al., 2008, Patel et al., 2017, Pirnot et al., 2016, Reznichenko and Hultzsch, 2016, Zi, 2009, Zi, 2011). In this context, transition-metal-catalyzed intermolecular asymmetric hydroamination of allenes (Berthold and Breit, 2018, Berthold et al., 2019, Cooke et al., 2012, Dion and Beauchemin, 2011, Lin et al., 2019, Parveen et al., 2017, Xu et al., 2016), alkynes (Athira et al., 2018, Liu et al., 2011, Lutete et al., 2004, Patil et al., 2006, Xu et al., 2019), and conjugated dienes (Adamson et al., 2017, Dion and Beauchemin, 2011, Lin et al., 2019, Löber et al., 2001, Park and Malcolmson, 2018, Xiong et al., 2018, Yang and Dong, 2017, Zhou and Hartwig, 2008) has been extensively studied (Figure 1B).…”

“…In this context, transition-metal-catalyzed intermolecular asymmetric hydroamination of allenes (Berthold and Breit, 2018, Berthold et al., 2019, Cooke et al., 2012, Dion and Beauchemin, 2011, Lin et al., 2019, Parveen et al., 2017, Xu et al., 2016), alkynes (Athira et al., 2018, Liu et al., 2011, Lutete et al., 2004, Patil et al., 2006, Xu et al., 2019), and conjugated dienes (Adamson et al., 2017, Dion and Beauchemin, 2011, Lin et al., 2019, Löber et al., 2001, Park and Malcolmson, 2018, Xiong et al., 2018, Yang and Dong, 2017, Zhou and Hartwig, 2008) has been extensively studied (Figure 1B). Nevertheless, the use of noble transition metals such as rhodium and palladium are often mandatory (Adamson et al., 2017, Aillaud et al., 2007, Athira et al., 2018, Berthold et al., 2019, Berthold and Breit, 2018, Clement and Jerome, 2017, Cooke et al., 2012, Dion and Beauchemin, 2011, Dondoni, 2015, Hannedouche and Schulz, 2013, Hannedouche and Schulz, 2018, Hii, 2006, Huang et al., 2015, Huo et al., 2019, Jerome, 2018, Lin et al., 2019, Liu et al., 2011, Löber et al., 2001, Lutete et al., 2004, Müller et al., 2008, Park and Malcolmson, 2018, Parveen et al., 2017, Patel et al., 2017, Patil et al., 2006, Pirnot et al., 2016, Reznichenko and Hultzsch, 2016, Xiong et al., 2018, Xu et al., 2016, Xu et al., 2019, Yang and Dong, 2017, Zhou and Hartwig, 2008, Zi, 2009, Zi, 2011); in addition, these methods suffer from limited amine scope (Adamson et al., 2017, Dion and Beauchemin, 2011, Lin et al., 2019, Löber et al., 2001, Park and Malcolmson, 2018, Xiong et al., 2018, Yang and Dong, 2017, Zhou and Hartwig, 2008), as well as excessive quantities of the unsaturated substrat...…”

Cobalt-Catalyzed Hydroamination of Alkenes with 5-Substituted Tetrazoles: Facile Access to 2,5-Disubstituted Tetrazoles and Asymmetric Intermolecular Hydroaminations

“…Finally, the amount of TMFP-BF 4 could be reduced to 1.5 eq without loss of yield (entry 11). It is worth noting that neither 1,5-disubstituted tetrazole 17,18) nor the anti-Markovnikov isomer were formed in these experiments.…”

Enhancing the catalytic properties of well-defined electrophilic platinum complexes

“…Hydroamination is an industrially valuable process that consists of the addition of a nucleophilic N-H functionality across a C-C multiple bond, giving rise to the corresponding C-N and C-H fragments. 74 Whereas this reaction has been widely studied with several catalytic systems, [75][76][77] there exist drawbacks arising from their sensitivity to oxygen and moisture and limited functional group compatibility. In light of this situation, late transition metal-based complexes have appeared as an efficient alternative in homogeneous catalysis.…”