A Practical Aryliodine(I/III) Catalysis for the Vicinal Diamination of Styrenes

Abstract

2,6‐Disubstituted iodoarenes bearing amide‐functionalized side arms are reported as new structures in redox‐active iodine(I/III) catalysis. In combination with bis‐sulfonimides as nitrogen sources and 3‐chloroperbenzoic acid (mCPBA) as benign terminal oxidant they catalyze the vicinal diamination of styrenes. The obtained reactivity and selectivity outperform other iodoarene catalyst candidates. This protocol provides a sustainable alternative to previous related protocols for diamination that are based on stoichiometric iodine(III) reagents.

Progress in organocatalysis with hypervalent iodine catalysts

“…Enantioselective diaminations of alkenes is typically performed with palladium, copper and titanium catalysts, 76–78 and lately Muñiz and colleagues have established an inexpensive route for the intermolecular diamination of styrenes 40 with bissulfonimides 41 as nitrogen source utilizing achiral as well as chiral aryl iodides as catalysts (Scheme 9). 79,80 They described the first iodine( iii )-catalysed enantioselective intermolecular diamination of styrenes 40 using chiral aryl iodide 42 as catalyst. 79 anti -Diamines 44 were obtained in moderate to good yields with high enantiomeric excess from both terminal as well as substituted styrenes.…”

“…Using achiral aryliodines 43a or 43b , irrespective of the position of substituents, styrenes 40 with various electron donating and electron withdrawing groups afforded diamine products 45 in good yields. 80 In addition to styrenes, diamination of ( E )-stilbene proceeded to afford diamines in moderate yield while allylbenzene produced the corresponding diamine in excellent yield.…”

Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives

“…Recently, hypervalent iodine­(III) reagents generated in situ through the oxidation of iodoarenes have been used as green alternatives to transition metals in the oxidative difunctionalization reaction- of alkenes . Based on this strategy, various iodoarene-catalyzed reactions have been developed, including aminofluorination, dioxygenation, diamination, difluorination, and others . Surprisingly, iodoarene-catalyzed oxyamination cyclizations that simultaneously generate both C–O and C–N bonds have rarely been reported.…”

Deciphering the Keys for High Enantioselectivity in Hypervalent Iodine-Catalyzed 1,2-Difunctionalization: Improved Synthesis of Ishihara–Muñiz Precatalysts

“…Asymmetric catalysis for vicinal transformations has become an increasingly important topic in recent years, especially for those involving 1,2-functionalizations. − In this matter, hypervalent iodine reagents and aryliodine precatalysts have remained an unchallenged source of innovation due to their broad reactivity and sustainability. − Similarly, oxidative transformations using these compounds have presented themselves as state-of-the-art, conveying high applicability in modern organic synthesis. , Additional focus was introduced by the development of asymmetric reactions using hypervalent iodine­(III) reagents or catalysts, which has led to crucial new developments in the past two decades. − …”