Hydroamination and Hydroaminoalkylation of Alkenes by Group 3–5 Elements: Recent Developments and Comparison with Late Transition Metals

Abstract

This short review highlights recent catalyst developments from Group III to V elements reported in the last few years to promote two highly atom-saving transformations, namely the hydroamination and hydroaminoalkylation, for the synthesis of both cyclic and acyclic nitrogen-containing compounds. A specific emphasis is given to reports leading to scalemic compounds essentially via intramolecular hydroamination catalyzed by Groups III-IV metals and intermolecular hydroaminoalkylation catalyzed by Group V elements. In both transformations, performances of these electropositive metals will be compared with recent developments obtained through late transition metals catalysis.

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).…”

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

“…Metal-catalyzed hydrofunctionalization of readily available alkenes with nitrogen sources is one of the most efficient methods for the synthesis of nitrogen-containing molecules; however, to achieve the high regio-and enantioselectivities of this transformation is still a challenge ( Fig. 2a) [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] . Among several activation strategies for alkene hydroamination, metal-catalyzed hydrogen atom transfer (HAT) reaction exhibits great Markovnikov selectivity and chemoselectivity (Fig.…”

Regio‐ and Enantioselective Formal Hydroamination of Enamines for the Synthesis of 1,2‐Diamines

“…Hydroamination is the direct formation of aC ÀNb ond by the formal addition of an NÀHb ond across either an alkene or an alkyne.T his effective strategy has attracted considerable attention from the scientific community over the past decade as it allows the rapid formation of either alkyl amines or enamines from readily available starting materials.T odate, significant progress has been made in the field of catalytic hydroamination, [1] and the reaction has been applied to av ariety of substrates. [2][3][4][5][6] As ar esult, the hydroamination reaction has been established as apowerful tool for the rapid synthesis of several types of amines,w hich themselves are valuable intermediates in organic and pharmaceutical chemistry.…”