Regio- and Stereoselective Synthesis of Diverse 3,4-Dihydro-2-quinolones through Catalytic Hydrative Cyclization of Imine- and Carbonyl-Ynamides with Water
Zhu, Bo-Han; Zhang, Ying-Qi; Xu, Hao-Jin; Li, Long; Deng, Guo-Cheng; Qian, Peng-Cheng; Deng, Chao; Ye, Long-Wu; ACS Catalysis  (2021) 1706–1713; doi:10.1021/acscatal.0c04786

data_4518414
_publ_section_title
;
 Regio- and Stereoselective Synthesis of Diverse 3,4-Dihydro-2-quinolones
 through Catalytic Hydrative Cyclization of Imine- and Carbonyl-Ynamides
 with Water
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1706
_journal_page_last               1713
_journal_paper_doi               10.1021/acscatal.0c04786
_journal_year                    2021
_chemical_formula_moiety         'C22 H18 Br N O4 S, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C22.5 H19 Br Cl N O4 S'
_chemical_formula_weight         514.81
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-31
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                82.566(5)
_cell_angle_beta                 83.909(5)
_cell_angle_gamma                87.659(5)
_cell_formula_units_Z            4
_cell_length_a                   12.185(3)
_cell_length_b                   12.529(4)
_cell_length_c                   14.695(4)
_cell_measurement_reflns_used    512
_cell_measurement_temperature    203
_cell_measurement_theta_max      21.945
_cell_measurement_theta_min      2.490
_cell_volume                     2211.2(11)
_computing_cell_refinement       'SAINT v6.28A (Bruker, 2002)'
_computing_data_reduction        'SAINT v6.28A (Bruker, 2002)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      203
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0467
_diffrn_reflns_av_unetI/netI     0.0841
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            16716
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.997
_diffrn_reflns_theta_min         1.405
_exptl_absorpt_coefficient_mu    2.104
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.740081
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS v.2.03 (Bruker,200?) was used for absorption correction.
R(int) was 0.1029 before and 0.0550 after correction.
The Ratio of minimum to maximum transmission is 0.7401.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       block
_exptl_crystal_F_000             1044
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.864
_refine_diff_density_min         -0.557
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         8422
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1056
_refine_ls_R_factor_gt           0.0724
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1290P)^2^+1.0190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2194
_refine_ls_wR_factor_ref         0.2345
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5417
_reflns_number_total             8422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c04786_si_005.cif
_cod_data_source_block           sad
_cod_original_formula_sum        'C22.50 H19 Br Cl N O4 S'
_cod_database_code               4518414
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C9A(H9A), C2(H2A), C2A(H2AB)
2.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB)
2.c Aromatic/amide H refined with riding coordinates:
 C11A(H11A), C13(H13), C11(H11), C14(H14), C8(H8), C22(H22), C13A(H13A),
 C17(H17), C5(H5), C21(H21), C6(H6), C7(H7), C14A(H14A), C4(H4), C18(H18),
 C22A(H22A), C21A(H21A), C4A(H4A), C5A(H5A), C6A(H6A), C18A(H18A), C8A(H8A),
 C17A(H17A), C7A(H7A)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F)
2.e Idealised tetrahedral OH refined as rotating group:
 O2A(H2AA), O2(H2)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'