1. Josiphos-type binaphane ligands for iridium-catalyzed enantioselective hydrogenation of 1-aryl-substituted dihydroisoquinolines.
Zhao Wei, Gang Zhou, Lin Yao, Shengyong Zhang, Huifang Nie, Yupu Zhu, Xiaomu Hu, Pingan Wang, Ru Jiang. Org Lett. 2019 Nov 1; 21(21): 8641-8645. DOI: 10.1021/acs.orglett.9b03251. PMID: 31603341.
Convenient synthesis and useful application of a series of Josiphos-type binaphane ligands were described. The iridium complexes of these chiral diphosphines displayed excellent enantioselectivity and good reactivity in the asymmetric hydrogenation of challenging 1-aryl-substituted dihydroisoquinoline substrates (full conversions, up to >99%ee, 4000 TON). The use of 40% HBr (aqueous solution) as an additive dramatically improved the asymmetric induction of these catalysts. This transformation provided a highly efficient and enantioselective access to chiral 1-aryl-substituted tetrahydroisoquinolines, which were of great importance and common in natural products and biologically active molecules.
2. From academia to the market - air-stable ni( ii)/josiphos catalysts.
Achim Link, Abderrahmane Amgoune, Florian Bächle, Anis Tlili. Chimia (Aarau). 2021 Nov 24; 75(11): 943-947. DOI: 10.2533/chimia.2021.943. PMID: 34798916.
The design, synthesis, commercialization and application of air-stable Ni(II)/Josiphos complexes has been realized in a collaboration between Solvias and ICBMS (University Lyon 1). The Ni-complexes are utilized as versatile precatalysts for diverse cross-coupling reactions. Apart from being active in established C-C and C-N couplings at low catalyst loadings, the novel Ni-precatalysts enabled the development of the challenging monoarylation of ammonia, ammonia surrogates and even alkylammonium chlorides with aryl carbamates. Finally, the α-arylation of acetone with aryl chlorides, carbamates and pivalates was demonstrated using the Ni(II)/Josiphos precatalysts.
