Formal Intermolecular Hydroamination of Unbiased Olefins for Primary Amine Formation

Abstract

A Pd/Ir dual metal tandem catalyst system was found to be active in catalyzing the one‐pot, two‐step formal hydroamination of unbiased olefins such as 1‐dodecene with an ammonia source to give branched primary amines in high yields of >85 % by using only 1 mol‐% of the Ir catalyst. This is the first report of the formal one‐pot intermolecular hydroamination of olefins to obtain primary amines.

Formal Enantioselective Hydroamination of Non‐Activated Alkenes: Transformation of Styrenes into Enantiomerically Pure 1‐Phenylethylamines in Chemoenzymatic One‐Pot Synthesis

“…Recently, we have demonstrated the suitability of such concept for the synthesis of chiral alcohols by combining a Pd‐/Cu‐catalyzed Wacker‐oxidation with ketone reduction using an alcohol dehydrogenase . Here we report a process that enables the direct transformation of styrene into enantiomerically pure 1‐phenyl‐ethylamine by combining Pd‐/Cu‐catalysts and a biocatalyst, thus corresponding to a “formal” enantioselective addition of ammonia to a non‐activated alkene (Scheme ) . The concept is also based on the use of a catalytic system instead of a monomolecular catalyst.…”

Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions

“…]azepin-2(3H)-one (3ac). 40 White solid (57.2 mg, 71%). 1 H NMR (CDCl 3, 400 MHz, ppm) δ 7.71 (dd, J = 1.4, 7.4 Hz, 1H), 7.41 (dt, J = 1.4, 7.4 Hz, 1H), 7.34 (dt, J = 1.2, 7.5 Hz, 1H), 7.19 (d, J = 7.5 Hz, 1H), 6.76 (br, 1H), 3.13 (q, J = 6.8 Hz, 2H), 2.87 (t, J = 7.1 Hz, 2H), 2.03 (quin, J = 7.1 Hz, 2H); 13 3-Hydroxy-13ot-amino-13,17-seco-1,3,5(10)-estratien-17-oic 13,17-Lactam (6).…”

“…H 2 18 O used was 99% 18 O-labeled water made by Taiyo Nippon Sanso Corporation. Most of the amides were characterized by 1 H NMR for comparison to previous reports. ,,,,,,− …”

Recent Developments in the Direct Synthesis of Unprotected Primary­ Amines

“…In 2015, Teo and co-workers realized the first catalytic synthesis of primary amines starting from a large set of terminal olefins (Scheme 4). 9 The overall process though occurs over two steps and does not install the desired functional group in a direct manner. First, a Wacker-type oxidation step in the presence of catalytic Pd and benzoquinone was necessary then the amine group was subsequently installed using ammonium formate as an ammonia equivalent and Xiao's Ir catalyzed reductive amination procedure (vide infra).…”