TY - JOUR
T1 - Ruthenium-catalyzed chemo-and enantioselective hydrogenation of isoquinoline carbocycles
AU - Jin, Yushu
AU - Makida, Yusuke
AU - Uchida, Tatsuya
AU - Kuwano, Ryoichi
N1 - Funding Information:
This work was partly supported by the JSPS KAKENHI Grants JP16H04149 and JP15KT0066. J.Y. thanks advanced Graduate Program on Molecular Systems for Devices, Program for Leading Graduate Schools for scholarship support. We thank the Cooperative Research Program of “Network Joint Research for Material and Devices” for HRMS measurements.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/4/6
Y1 - 2018/4/6
N2 - A chemoselective hydrogenation of isoquinoline carbocycles was achieved by using the catalyst prepared from Ru(methallyl)2(cod) and trans-chelate chiral ligand PhTRAP. The unique chemoselectivity achieved in this hydrogenation could be ascribed to the trans-chelation of the chiral ligand. The procedure for preparing the catalyst strongly affects the reproducibility of the carbocycle hydrogenation. Various 5-, 6-, 7-, and 8-substituted isoquinolines were selectively hydrogenated at their carbocycles to afford 5,6,7,8-tetrahydroisoquinolines as major products in high yields with moderate or good enantioselectivities. Some mechanistic studies suggested that the stereogenic center was created during the initial addition of H2 to the aromatic ring in the hydrogenation of 5-substituted isoquinolines. In other words, the stereochemical control was accompanied by the dearomatization.
AB - A chemoselective hydrogenation of isoquinoline carbocycles was achieved by using the catalyst prepared from Ru(methallyl)2(cod) and trans-chelate chiral ligand PhTRAP. The unique chemoselectivity achieved in this hydrogenation could be ascribed to the trans-chelation of the chiral ligand. The procedure for preparing the catalyst strongly affects the reproducibility of the carbocycle hydrogenation. Various 5-, 6-, 7-, and 8-substituted isoquinolines were selectively hydrogenated at their carbocycles to afford 5,6,7,8-tetrahydroisoquinolines as major products in high yields with moderate or good enantioselectivities. Some mechanistic studies suggested that the stereogenic center was created during the initial addition of H2 to the aromatic ring in the hydrogenation of 5-substituted isoquinolines. In other words, the stereochemical control was accompanied by the dearomatization.
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U2 - 10.1021/acs.joc.8b00190
DO - 10.1021/acs.joc.8b00190
M3 - Article
C2 - 29547282
AN - SCOPUS:85045089078
VL - 83
SP - 3829
EP - 3839
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 7
ER -