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_4518412
_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         '2(C26 H26 Br F N2 O4 S2)'
_chemical_formula_sum            'C52 H52 Br2 F2 N4 O8 S4'
_chemical_formula_weight         1187.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_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                 105.257(3)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   12.9016(4)
_cell_length_b                   9.0322(2)
_cell_length_c                   12.9338(3)
_cell_measurement_reflns_used    13488
_cell_measurement_temperature    105(9)
_cell_measurement_theta_max      76.0500
_cell_measurement_theta_min      3.5420
_cell_volume                     1454.05(7)
_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      105(9)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.962
_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     35.00  77.00   0.50    1.19    --   46.62  26.00 -47.00   84
  2  \w     78.00 108.00   0.50    1.19    --   46.62  26.00 -47.00   60
  3  \w     95.00 128.00   0.50    5.00    --  108.56  26.00 -47.00   66
  4  \w    146.00 173.00   0.50    5.00    --  108.56  26.00 -47.00   54
  5  \w    118.00 174.00   0.50    5.00    --  108.56  77.00-180.00  112
  6  \w     93.00 160.00   0.50    5.00    --  108.56 125.00-150.00  134
  7  \w    147.00 178.00   0.50    5.00    --  108.56 125.00   0.00   62
  8  \w     98.00 178.00   0.50    5.00    --  108.56  30.00  60.00  160
  9  \w     97.00 122.00   0.50    5.00    --  108.56 -77.00 -30.00   50
 10  \w     88.00 114.00   0.50    5.00    --  108.56-125.00   0.00   52
 11  \w     54.00 115.00   0.50    5.00    --  108.56-125.00  60.00  122
 12  \w     34.00 123.00   0.50    5.00    --  108.56 -26.00 148.00  178
 13  \w     92.00 119.00   0.50    1.19    --   46.62  77.00  90.00   54
 14  \w     94.00 119.00   0.50    5.00    --  108.56 125.00   0.00   50
 15  \w     32.00  72.00   0.50    1.19    --   46.62  57.00   0.00   80
 16  \w     32.00  59.00   0.50    1.19    --   46.62  57.00 -60.00   54
 17  \w     24.00  61.00   0.50    1.19    --   46.62  77.00 -30.00   74
 18  \w     31.00 118.00   0.50    1.19    --   46.62  19.00-150.00  174
 19  \w     66.00 119.00   0.50    1.19    --   46.62  77.00-180.00  106
 20  \w     23.00  60.00   0.50    1.19    --   46.62  77.00-180.00   74
 21  \w    -42.00 -15.00   0.50    1.19    --  -46.62  26.00 -47.00   54
 22  \w    -98.00 -58.00   0.50    5.00    --  -88.50  26.00 -47.00   80
 23  \w    -90.00 -35.00   0.50    1.19    --  -46.62 -37.00  90.00  110
 24  \w    -63.00 -33.00   0.50    1.19    --  -46.62 -26.00 148.00   60
 25  \w     23.00  49.00   0.50    1.19    --   46.62  77.00  90.00   52
 26  \w     25.00  65.00   0.50    1.19    --   46.62  77.00 120.00   80
 27  \w     -8.00  17.00   0.50    1.19    --   46.62 -26.00 148.00   50
 28  \w     36.00  99.00   0.50    5.00    --  108.56 -94.00 150.00  126
 29  \w     36.00 102.00   0.50    5.00    --  108.56 -94.00 120.00  132
 30  \w     37.00  84.00   0.50    5.00    --  108.56-125.00   0.00   94
 31  \w     46.00 107.00   0.50    5.00    --  108.56 -94.00 -90.00  122
 32  \w     37.00 107.00   0.50    5.00    --  108.56 -94.00-180.00  140
 33  \w     33.00  94.00   0.50    1.19    --   46.62-125.00-180.00  122
 34  \w     38.00  83.00   0.50    5.00    --  108.56 -77.00 -30.00   90
 35  \w    -50.00 -24.00   0.50    1.19    --  -46.62 -77.00-120.00   52
 36  \w    -51.00 -26.00   0.50    1.19    --  -46.62 -77.00-150.00   50
 37  \w    -60.00 -23.00   0.50    1.19    --  -46.62 -77.00-180.00   74
 38  \w    -60.00 -23.00   0.50    1.19    --  -46.62 -77.00 -60.00   74
 39  \w    -77.00 -23.00   0.50    1.19    --  -46.62 -77.00   0.00  108
 40  \w    -73.00 -23.00   0.50    1.19    --  -46.62 -77.00  60.00  100
 41  \w    -93.00 -64.00   0.50    5.00    --  -88.50 -79.00 101.61   58
 42  \w    -93.00 -66.00   0.50    5.00    --  -88.50 -73.00 120.77   54
 43  \w    -93.00 -65.00   0.50    5.00    --  -88.50 -77.00  60.00   56
 44  \w    -91.00 -62.00   0.50    5.00    --  -88.50 -82.00   1.99   58
 45  \w    -89.00 -63.00   0.50    5.00    --  -88.50 -80.00 -47.94   52
 46  \w   -103.00 -67.00   0.50    5.00    --  -88.50 -70.00-121.49   72
 47  \w    -95.00 -63.00   0.50    5.00    --  -88.50 -80.00-171.00   64
 48  \w    -90.00 -63.00   0.50    5.00    --  -88.50 -82.00-119.85   54
 49  \w   -107.00 -64.00   0.50    5.00    --  -88.50 -79.00-146.05   86
 50  \w   -106.00 -69.00   0.50    5.00    --  -88.50 -65.00-179.34   74
 51  \w   -112.00 -64.00   0.50    5.00    --  -88.50 -79.00 -70.78   96
 52  \w    -97.00 -65.00   0.50    5.00    --  -88.50 -75.00 -22.37   64
 53  \w    -90.00 -64.00   0.50    5.00    --  -88.50 -78.00  39.41   52
 54  \w    -89.00 -63.00   0.50    5.00    --  -88.50 -80.00  80.85   52
 55  \w   -106.00 -68.00   0.50    5.00    --  -88.50 -77.00  90.00   76
 56  \w   -113.00 -78.00   0.50    1.19    --  -46.62 -26.00 148.00   70
 57  \w   -118.00 -81.00   0.50    1.19    --  -46.62 -77.00  60.00   74
 58  \w   -115.00 -62.00   0.50    5.00    --  -88.50 -83.00 119.83  106
 59  \w   -123.00 -64.00   0.50    5.00    --  -88.50 -79.00 178.11  118
 60  \w   -143.00 -77.00   0.50    5.00    --  -88.50 -26.00 148.00  132
 61  \w   -135.00 -68.00   0.50    5.00    --  -88.50 -68.00  35.97  134
 62  \w   -112.00 -85.00   0.50    1.19    --  -46.62 -77.00 -60.00   54
 63  \w   -114.00 -63.00   0.50    5.00    --  -88.50 -81.00 -29.92  102
 64  \w   -137.00 -65.00   0.50    5.00    --  -88.50 -77.00 -90.00  144
 65  \w   -153.00 -64.00   0.50    5.00    --  -88.50 -78.00 -98.65  178
 66  \w   -152.00-117.00   0.50    5.00    --  -88.50 -81.00 -29.92   70
 67  \w   -153.00 -66.00   0.50    5.00    --  -88.50 -74.00  13.28  174
 68  \w   -149.00 -65.00   0.50    5.00    --  -88.50 -77.00  30.00  168
 69  \w   -159.00-126.00   0.50    5.00    --  -88.50 -79.00-146.05   66
 70  \w   -160.00-116.00   0.50    5.00    --  -88.50 -82.00-119.85   88
 71  \w   -160.00-116.00   0.50    5.00    --  -88.50 -80.00 -47.94   88
 72  \w   -151.00-102.00   0.50    5.00    --  -88.50 -75.00 -22.37   98
 73  \w   -156.00-130.00   0.50    5.00    --  -88.50 -77.00  60.00   52
 74  \w   -160.00 -64.00   0.50    5.00    --  -88.50 -79.00 143.02  192
 75  \w   -159.00 -65.00   0.50    5.00    --  -88.50 -75.00 152.85  188
 76  \w    -91.00 -19.00   0.50    1.19    --  -46.62 125.00-180.00  144
;
_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      0.0489797000
_diffrn_orient_matrix_UB_12      -0.1228464000
_diffrn_orient_matrix_UB_13      0.0807063000
_diffrn_orient_matrix_UB_21      0.0466554000
_diffrn_orient_matrix_UB_22      0.1181726000
_diffrn_orient_matrix_UB_23      0.0854862000
_diffrn_orient_matrix_UB_31      -0.1036830000
_diffrn_orient_matrix_UB_32      -0.0048882000
_diffrn_orient_matrix_UB_33      0.0377420000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0739
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            33717
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.774
_diffrn_reflns_theta_min         3.542
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.597
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83229
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.222
_refine_diff_density_min         -0.674
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details
;
 Flack x determined using 2318 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.036(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         5729
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0802
_refine_ls_R_factor_gt           0.0742
_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^)+(0.1155P)^2^+2.4663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1890
_refine_ls_wR_factor_ref         0.1931
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.903
_reflns_number_gt                5441
_reflns_number_total             5729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c04786_si_003.cif
_cod_data_source_block           exp_8418
_cod_database_code               4518412
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.533
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C00X) \\sim Ueq, Uanis(C00Y) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
3. Others
 Fixed Sof: Br1(0.5) Br2(0.5)
4.a Ternary CH refined with riding coordinates:
 C00H(H00H), C00Q(H00Q)
4.b Aromatic/amide H refined with riding coordinates:
 N007(H007), C00F(H00F), C00G(H00G), C00M(H00M), C00N(H00N), C00O(H00O),
 C00S(H00S), C00T(H00T), C00U(H00U), C00V(H00V), C00Y(H00Y), C00Z(H00Z)
4.c Idealised Me refined as rotating group:
 C00I(H00A,H00B,H00C), C00K(H00D,H00E,H00I), C00L(H00J,H00K,H00L), 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 1.583
_oxdiff_exptl_absorpt_empirical_full_min 0.357