Metal-Free, n-Bu₄NI-Catalyzed Regioselective Difunctionalization of Unactivated Alkenes

Abstract

A new synthetic approach toward difunctionalization of alkenes has been developed under metal-free conditions. Various carboxylic acids and amines could react smoothly with alkenes to give dioxygenation and oxyamidation products, respectively. This organocatalytic process delivers 2-hydroxy alcohols directly from simple alkenes with high levels of region control.

Recent Advances in Radical Dioxygenation of Olefins

“…[36] In this catalytic system, styrenes bearing electron-withdrawing groups were more effective substrates than those with electron-donating groups. [36] In this catalytic system, styrenes bearing electron-withdrawing groups were more effective substrates than those with electron-donating groups.…”

“…[36] tert-Butoxyl and tert-butylperoxy radicals, generated with a nBu 4 NI/ TBHP system, reacted with the acids to afford radicals a, which further reacted with the olefins, with subsequent oxidation, to give the benzyl cations c. These and water furnished the desired products. [36] tert-Butoxyl and tert-butylperoxy radicals, generated with a nBu 4 NI/ TBHP system, reacted with the acids to afford radicals a, which further reacted with the olefins, with subsequent oxidation, to give the benzyl cations c. These and water furnished the desired products.…”

Hypervalent Iodine‐Catalyzed Oxidative Functionalizations Including Stereoselective Reactions

“…This catalytic approach provides selective synthesis of a broad range of linear aryl and alkyl α,β‐unsaturated ketones 107 in moderate yields (Scheme ). Zhu and co‐workers reported the n Bu 4 NI‐catalyzed regioselective difunctionalization of unactivated alkenes using tert ‐butylperoxide as oxidant, however, a hypervalent iodine species was not generated during this transformation 55…”

Direkte katalytische Synthese von ungeschützten 2‐Amino‐1‐phenylethanolen aus Alkenen mithilfe von Eisen(II)‐phthalocyanin

“…[4][5][6][7][8] Viele Tr ansformationen, darunter Fe-u nd Cu-katalysierte Reaktionen, die Alkene und Hydroxylamin-abgeleitete Reagentien umsetzen, stellen die Schutzgruppe,d ie den Aminoalkohol beinhaltet, sowohl am N-als auch am O-Atom bereit. [4] Alternativ wurden Verfahren entwickelt, die nur das N-Atom in der geschützten Form einführen.…”

“…[4] Alternativ wurden Verfahren entwickelt, die nur das N-Atom in der geschützten Form einführen. [5] Darunter ist die Os-katalysierte Aminohydroxylierung immer noch die am häufigsten genutzte Methode,u mA minoalkohol-Derivate aus Alkenen zugänglich zu machen. Ein neueres Beispiel stellt der Bericht eines Mnkatalysierten zweistufigen Prozess dar,d er die Synthese von Azidoalkoholen ermçglicht.…”