Catalytic, Enantioselective Diamination of Alkenes

Abstract

Enantioselective diamination of alkenes represents one of the most straightforward methods to access enantioenriched, vicinal diamines, which are not only frequently encountered in biologically active compounds, but also have broad applications in asymmetric synthesis. Although the analogous dihydroxylation of olefins is well-established, the development of enantioselective olefin diamination lags far behind. Nevertheless, several successful methods have been developed that operate by different reaction mechanisms, including a cycloaddition pathway, a two-electron redox pathway, and a radical pathway. This short review summarizes recent advances and identifies limitations, with the aim of inspiring further developments in this area.1 Introduction2 Cycloaddition Pathway3 Two-Electron Redox Pathway3.1 Pd(0)/Pd(II) Diamination3.2 Pd(II)/Pd(IV) Diamination3.3 I(I)/I(III) Diamination3.4 Se(II)/Se(IV) Diamination4 One-Electron Radical Pathway4.1 Cu-Catalyzed Diamination4.2 Fe-Catalyzed Diamination5 Summary and Outlook

Synthesis of 3‐Aminopiperidines via I(III)‐Mediated Olefin Diamination with (Hetero)aryl Nucleophiles

“…An attractive approach to the 3‐aminopiperdine motif is the 6‐endo diamination of olefins using an exogenous amine nucleophile, but achieving selectivity for 6‐endo over 5‐exo cyclization is a significant challenge as both pathways are favorable, with 5‐exo being predominant [3–16] . While advancements in achieving 6‐endo selectivity in olefin aminohalogenation [17–20] and aminoxygenation [21–24] have been made, diamination remains a significant challenge.…”

“…An attractive approach to the 3-aminopiperdine motif is the 6-endo diamination of olefins using an exogenous amine nucleophile, but achieving selectivity for 6-endo over 5-exo cyclization is a significant challenge as both pathways are favorable, with 5-exo being predominant. [3][4][5][6][7][8][9][10][11][12][13][14][15][16] While advancements in achiev-ing 6-endo selectivity in olefin aminohalogenation [17][18][19][20] and aminoxygenation [21][22][23][24] have been made, diamination remains a significant challenge. There have been reports on the use of Au [25] and Pd [26,27] catalysis, however these rely on expensive precious metal catalysts and are limited in exogenous amine scope to either nitrile nucleophiles (4) or NFSI as an electrophilic amine source to give bis(sulfonyl)imides (5), respectively (Scheme 1A).…”

“…[3][4][5][6][7][8][9][10][11][12][13][14][15][16] While advancements in achiev-ing 6-endo selectivity in olefin aminohalogenation [17][18][19][20] and aminoxygenation [21][22][23][24] have been made, diamination remains a significant challenge. There have been reports on the use of Au [25] and Pd [26,27] catalysis, however these rely on expensive precious metal catalysts and are limited in exogenous amine scope to either nitrile nucleophiles (4) or NFSI as an electrophilic amine source to give bis(sulfonyl)imides (5), respectively (Scheme 1A).…”

Photoinduced EnT-mediated sulfonamidylimination of alkenes and (hetero)arenes with iminophenylacetic acid oxime esters

“…1 Due to their abundance, ready accessibility, and diverse reactivity, alkenes are recognized as fundamental components in organic chemistry, and the synthesis of the corresponding vicinal diamines via diamination of alkenes constitutes an attractive method. 2 However, these reactions frequently require esoteric or toxic nitrogenous reagents ( e.g. , nitrogen oxides, 3 diaziridinones, 4 N -activated sulfamides, 5 TMSN 3 6 and NaN 3 7 ) or external stoichiometric oxidant.…”

Regioselective Synthesis of Unsymmetrical Vicinal Diamines via Azidoimination of Alkenes with TMSN3 and Ketimines

“…Consequently, the expedient assembly of vicinal diamines from readily available precursors has long been recognized as a preeminent goal in organic synthesis. In this context, the diamination of carbon–carbon double bonds represent straightforward routes to an array of such useful scaffolds and has been of great interest to those working in synthetic chemistry, given the facile accessibility of alkene starting materials and quickly increasing molecular complexity in a single operation . Despite tremendous progress made in these areas, the synthetic utility often suffers from the need for harsh conditions, stoichiometric amounts of organometallic reagents, expensive transition-metal catalysts, and photochemical/electrochemical ancillaries, which leads to issues on cost, the environment, and operational inconveniences.…”