Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles† †Electronic supplementary information (ESI) available: 1H and 13C{1H} NMR spectra and HPLC traces of all novel compounds. Coordinates, thermal corrections, and energies of all computed structures. See DOI: 10.1039/c6sc00940a Click here for additional data file. Click here for additional data file.
نویسندگان
چکیده
Isothiourea-catalyzed annulations between 2-acyl benzazoles and a,b-unsaturated acyl ammonium intermediates are selectively tuned to form either lactam or lactone heterocycles in good yields (up to 95%) and high ee (up to 99%) using benzothiazole or benzoxazole derivatives, respectively. Computation gives insight into the significant role of two 1,5-S/O interactions in controlling the structural preorganization and chemoselectivity observed within the lactam synthesis with benzothiazoles as nucleophiles. When using benzazoles the absence of a second stabilizing non-bonding 1,5-S/O interaction leads to a dominant C–H/O interaction in determining structural preorganization and lactone formation.
منابع مشابه
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