pH-Mediated Selective Synthesis of N-Allylic Alkylation or N-Alkylation Amines with Allylic Alcohols via an Iridium Catalyst in Water

Abstract

Amination of allylic alcohols is an effective approach in the facile synthesis of N-allylic alkylation or N-alkylation amines. Recently, a series of catalysts were devised to push forward this transformation. However, current synthetic methods are typically limited to achieve either N-allylic alkylation or N-alkylation products via a certain catalyst. In this article, a pH-mediated selective synthesis of N-allylic alkylation or N-alkylation amines with allylic alcohols via an iridium catalyst with water as the environmental benign solvent is revealed, enabling the miscellaneous synthesis of N-allylic alkylation and N-alkylation products in outstanding yields. Furthermore, a gram-scale experiment with low catalyst loading offers the potential to access a distinct entry for the synthesis of the antifungal drug naftifine.

Synthesis of N-alkoxy amines and hydroxylamines via the iridium-catalyzed transfer hydrogenation of oximes

“…Based on the experimental observations, mechanistic investigations, and previous studies of TCs, 26 an outer sphere mechanism was proposed for the transfer hydrogenation (Scheme 8). 31 Firstly, HCO 2 H is decomposed by TC with the release of CO 2 .…”

“…Previously we reported a series of efficient transfer hydrogenation methods for CC, CO and CN bonds based on Ir catalyst systems. 26 Building upon this, we proposed that effective access to N -alkoxy amines and hydroxylamines could be achieved by transfer hydrogenation of the corresponding oximes. In addition, the application of transfer hydrogenation to oximes provided an opportunity to improve its practicality by increasing the catalytic efficiency/selectivity and promoting milder reaction conditions.…”

Iridium-Catalyzed Acceptorless Dehydrogenative Coupling of 2-Aminoarylmethanols with Amides or Nitriles to Synthesize Quinazolines

“…Based on the experiment results and literature, 22 a plausible mechanism is proposed for this iridium-catalyzed ADC transformation (Scheme 5 ). First, the Int-I is formed by the ‘borrowing hydrogen’ process under the interaction of TC-6 with 1 , 22a e which undergoes β-H elimination to form Int-II and 2-aminobenzaldehyde ( 6 ). In this process, the dehydrogenation of benzyl alcohol to form the amount of liberated H 2 was determined by previous literature.…”

Enzymatic N-Allylation of Primary and Secondary Amines Using Renewable Cinnamic Acids Enabled by Bacterial Reductive Aminases

“…As a consequence, recent efforts have favored the use of greener reagents such as allylic alcohols, 33 with several groups demonstrating the direct use of allylic alcohols as allylating substrates with/without Lewis acid activators ( Figure 1 c). 12 , 21 , 27 , 30 , 31 , 34 , 35 …”