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_4518413
_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_absolute_configuration ad
_chemical_formula_moiety         'C26 H28 N2 O4 S2, C H2 Cl2'
_chemical_formula_sum            'C27 H30 Cl2 N2 O4 S2'
_chemical_formula_weight         581.55
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.35619(4)
_cell_length_b                   16.99000(7)
_cell_length_c                   17.21824(8)
_cell_measurement_reflns_used    60084
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      76.4730
_cell_measurement_theta_min      3.6350
_cell_volume                     2737.04(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -66.00 -31.00   0.50    0.05    --  -46.81 -30.00  44.00   70
  2  \w    -61.00  -7.00   0.50    0.05    --  -46.81  30.00-155.00  108
  3  \w     -2.00  26.00   0.50    0.05    --  -46.81  30.00-155.00   56
  4  \w   -117.00 -76.00   0.50    0.05    --  -46.81 -30.00  44.00   82
  5  \w     36.00  89.00   0.50    0.05    --   46.81  30.00-155.00  106
  6  \w    -59.00 -26.00   0.50    0.05    --  -88.50  30.00-155.00   66
  7  \w   -162.00-121.00   0.50    0.05    --  -88.50 -30.00  44.00   82
  8  \w     93.00 159.00   0.50    0.05    --  108.56  30.00-155.00  132
  9  \w   -113.00 -86.00   0.50    0.05    --  -46.81 -77.00   0.00   54
 10  \w    -58.00 -24.00   0.50    0.05    --  -46.81 -77.00 -90.00   68
 11  \w   -104.00 -78.00   0.50    0.05    --  -46.81 -77.00-150.00   52
 12  \w   -121.00 -95.00   0.50    0.05    --  -46.81 -19.00  90.00   52
 13  \w    -73.00 -23.00   0.50    0.05    --  -46.81 -77.00  60.00  100
 14  \w   -119.00 -78.00   0.50    0.05    --  -46.81 -77.00  60.00   82
 15  \w   -112.00 -86.00   0.50    0.05    --  -46.81 -77.00 120.00   52
 16  \w    -62.00 -23.00   0.50    0.05    --  -46.81 -77.00-180.00   78
 17  \w   -116.00 -91.00   0.50    0.05    --  -46.81 -77.00 -60.00   50
 18  \w   -110.00 -81.00   0.50    0.05    --  -46.81 -77.00-180.00   58
 19  \w    -58.00 -23.00   0.50    0.05    --  -46.81 -77.00   0.00   70
 20  \w    -84.00 -31.00   0.50    0.05    --  -46.81 -19.00  90.00  106
 21  \w    -52.00 -23.00   0.50    0.05    --  -46.81 -77.00 120.00   58
 22  \w    -48.00 -23.00   0.50    0.05    --  -46.81 -77.00-150.00   50
 23  \w    -63.00 -23.00   0.50    0.05    --  -46.81 -77.00 -60.00   80
 24  \w     31.00  70.00   0.50    0.05    --   46.81  57.00 -60.00   78
 25  \w     38.00  96.00   0.50    0.05    --   46.81-125.00   0.00  116
 26  \w     32.00  94.00   0.50    0.05    --   46.81-125.00 -60.00  124
 27  \w     95.00 120.00   0.50    0.05    --   46.81  57.00 -60.00   50
 28  \w     23.00  53.00   0.50    0.05    --   46.81  77.00-150.00   60
 29  \w     16.00  50.00   0.50    0.05    --   46.81 -30.00  44.00   68
 30  \w     90.00 115.00   0.50    0.05    --   46.81  37.00 -90.00   50
 31  \w     33.00  85.00   0.50    0.05    --   46.81  37.00 -90.00  104
 32  \w     31.00  57.00   0.50    0.05    --   46.81  57.00   0.00   52
 33  \w    -25.00   1.00   0.50    0.05    --   46.81 -30.00  44.00   52
 34  \w   -160.00 -65.00   0.50    0.05    --  -88.50 -75.00 -23.01  190
 35  \w   -107.00 -64.00   0.50    0.05    --  -88.50 -79.00-123.33   86
 36  \w   -119.00 -65.00   0.50    0.05    --  -88.50 -77.00 150.00  108
 37  \w   -159.00 -65.00   0.50    0.05    --  -88.50 -75.00 161.82  188
 38  \w    -87.00 -62.00   0.50    0.05    --  -88.50 -82.00  75.93   50
 39  \w   -146.00-120.00   0.50    0.05    --  -88.50 -79.00-123.33   52
 40  \w   -106.00 -62.00   0.50    0.05    --  -88.50 -83.00  58.87   88
 41  \w   -159.00-133.00   0.50    0.05    --  -88.50 -79.00 158.24   52
 42  \w    -90.00 -65.00   0.50    0.05    --  -88.50 -77.00 -30.00   50
 43  \w   -109.00 -65.00   0.50    0.05    --  -88.50 -77.00-120.00   88
 44  \w   -160.00 -65.00   0.50    0.05    --  -88.50 -77.00  36.29  190
 45  \w   -147.00-121.00   0.50    0.05    --  -88.50 -77.00 150.00   52
 46  \w    -95.00 -65.00   0.50    0.05    --  -88.50 -77.00   0.00   60
 47  \w    -90.00 -64.00   0.50    0.05    --  -88.50 -82.00 -41.63   52
 48  \w   -145.00 -66.00   0.50    0.05    --  -88.50 -73.00 130.30  158
 49  \w    -95.00 -63.00   0.50    0.05    --  -88.50 -80.00 101.47   64
 50  \w   -156.00-103.00   0.50    0.05    --  -88.50 -80.00 101.47  106
 51  \w    -88.00 -63.00   0.50    0.05    --  -88.50 -80.00-159.93   50
 52  \w   -121.00 -65.00   0.50    0.05    --  -88.50 -77.00-150.00  112
 53  \w   -157.00-123.00   0.50    0.05    --  -88.50 -78.00 -61.48   68
 54  \w   -116.00 -64.00   0.50    0.05    --  -88.50 -78.00 -61.48  104
 55  \w   -157.00-129.00   0.50    0.05    --  -88.50 -77.00-150.00   56
 56  \w   -143.00-114.00   0.50    0.05    --  -88.50 -80.00-159.93   58
 57  \w   -116.00 -62.00   0.50    0.05    --  -88.50 -83.00  69.77  108
 58  \w   -160.00 -65.00   0.50    0.05    --  -88.50 -75.00 -96.81  190
 59  \w    -88.00 -63.00   0.50    0.05    --  -88.50 -80.00-179.93   50
 60  \w   -133.00 -65.00   0.50    0.05    --  -88.50 -77.00  30.00  136
 61  \w   -159.00-133.00   0.50    0.05    --  -88.50 -80.00-179.93   52
 62  \w    -89.00 -64.00   0.50    0.05    --  -88.50 -79.00 158.24   50
 63  \w   -115.00 -62.00   0.50    0.05    --  -88.50 -82.00  89.56  106
 64  \w   -149.00 -66.00   0.50    0.05    --  -88.50 -77.00 -82.79  166
 65  \w   -116.00 -64.00   0.50    0.05    --  -88.50 -78.00 110.03  104
 66  \w   -154.00-110.00   0.50    0.05    --  -88.50 -83.00  58.87   88
 67  \w   -160.00-135.00   0.50    0.05    --  -88.50 -82.00  89.56   50
 68  \w    -88.00 -63.00   0.50    0.05    --  -88.50 -80.00-135.05   50
 69  \w   -123.00 -98.00   0.50    0.05    --  -88.50 -83.00 131.72   50
 70  \w    -87.00 -62.00   0.50    0.05    --  -88.50 -83.00 131.72   50
 71  \w   -128.00 -66.00   0.50    0.05    --  -88.50 -79.00  -2.82  124
 72  \w   -159.00 -67.00   0.50    0.05    --  -88.50 -71.00   5.58  184
 73  \w   -130.00 -62.00   0.50    0.05    --  -88.50 -82.00 -34.95  136
 74  \w   -122.00 -64.00   0.50    0.05    --  -88.50 -78.00 -73.87  116
 75  \w    -91.00 -22.00   0.50    0.05    --  -88.50 125.00 -90.00  138
 76  \w   -112.00 -64.00   0.50    0.05    --  -88.50 -78.00-105.32   96
 77  \w   -132.00-107.00   0.50    0.05    --  -88.50 -82.00 -41.63   50
 78  \w     92.00 123.00   0.50    0.05    --  108.56 -45.00 -60.00   62
 79  \w     39.00  86.00   0.50    0.05    --  108.56 -45.00 -60.00   94
 80  \w     37.00 106.00   0.50    0.05    --  108.56 -94.00  90.00  138
 81  \w     61.00  91.00   0.50    0.05    --  108.56 -94.00   0.00   60
 82  \w     38.00 124.00   0.50    0.05    --  108.56 -30.00  44.00  172
 83  \w     39.00 116.00   0.50    0.05    --  108.56-125.00 -90.00  154
 84  \w     36.00 106.00   0.50    0.05    --  108.56 -94.00-150.00  140
 85  \w     93.00 164.00   0.50    0.05    --  108.56 125.00  30.00  142
 86  \w     38.00 130.00   0.50    0.05    --  108.56 -77.00  90.00  184
 87  \w     41.00 108.00   0.50    0.05    --  108.56 -94.00 -60.00  134
 88  \w     36.00 100.00   0.50    0.05    --  108.56 -94.00  30.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0384316000
_diffrn_orient_matrix_UB_12      -0.0858763000
_diffrn_orient_matrix_UB_13      -0.0196787000
_diffrn_orient_matrix_UB_21      -0.1539049000
_diffrn_orient_matrix_UB_22      0.0141228000
_diffrn_orient_matrix_UB_23      0.0285906000
_diffrn_orient_matrix_UB_31      -0.0441791000
_diffrn_orient_matrix_UB_32      0.0253730000
_diffrn_orient_matrix_UB_33      -0.0824828000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            79345
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.221
_diffrn_reflns_theta_min         3.655
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.862
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69838
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       block
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.495
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 2317 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         5623
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0267
_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^)+(0.0456P)^2^+0.7022P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0669
_refine_ls_wR_factor_ref         0.0684
_reflns_Friedel_coverage         0.746
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                5513
_reflns_number_total             5623
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c04786_si_004.cif
_cod_data_source_block           exp_8455
_cod_database_code               4518413
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.512
_shelx_estimated_absorpt_t_min   0.390
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00E(H00E), C00M(H00M)
2.b Secondary CH2 refined with riding coordinates:
 C011(H01D,H01E)
2.c Aromatic/amide H refined with riding coordinates:
 N009(H009), C00C(H00C), C00G(H00G), C00J(H00J), C00L(H00L), C00N(H00N),
 C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T),
 C00V(H00V), C00W(H00W)
2.d Idealised Me refined as rotating group:
 C00X(H00A,H00B,H00D), C00Y(H00F,H00H,H00I), C00Z(H00K,H00U,H00X), C010(H01A,
 H01B,H01C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.719
_oxdiff_exptl_absorpt_empirical_full_min 0.784