Enantioselective C–H bond functionalization of aromatic ketones with 1,6-enynes via photoredox/cobalt dual catalysis
Maji, Kakoli; Thorve, Pradip Ramdas; Rai, Pramod; Maji, Biplab; Chemical Communications  (2022) –; doi:10.1039/D2CC03595B

data_7130469
_publ_section_title
;
 Enantioselective C--H bond functionalization of aromatic ketones with
 1,6-enynes via photoredox/cobalt dual catalysis
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03595B
_journal_year                    2022
_chemical_formula_moiety         'C29 H31 N O3 S'
_chemical_formula_sum            'C29 H31 N O3 S'
_chemical_formula_weight         473.61
_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             2022-01-02
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-01-02 deposited with the CCDC.	2022-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                109.579(2)
_cell_angle_beta                 91.015(2)
_cell_angle_gamma                93.297(2)
_cell_formula_units_Z            2
_cell_length_a                   9.0088(2)
_cell_length_b                   11.8283(2)
_cell_length_c                   12.2176(2)
_cell_measurement_reflns_used    11277
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      66.5320
_cell_measurement_theta_min      3.8340
_cell_volume                     1223.64(4)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.9863
_diffrn_measured_fraction_theta_max 0.9995
_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    -24.00  35.00   0.50    0.20    --  -40.33  12.00 -30.00  118
  2  \w    -24.00  35.00   0.50    0.20    --  -40.33  12.00  30.00  118
  3  \w    -24.00  35.00   0.50    0.20    --  -40.33  12.00  90.00  118
  4  \w    -26.00  43.00   0.50    0.20    --   40.33 -38.00   0.00  138
  5  \w     31.00  88.00   0.50    0.20    --   40.33-121.00 -41.00  114
  6  \w     41.00  99.00   0.50    0.20    --   40.33-138.00-120.00  116
  7  \w     44.00 127.00   0.50    0.90    --   96.67-145.00 -90.00  166
  8  \w     44.00 127.00   0.50    0.90    --   96.67-145.00  60.00  166
  9  \w     48.00 109.00   0.50    0.20    --   40.33-153.00 159.00  122
 10  \w     48.00 132.00   0.50    0.90    --   96.67-153.00 159.00  168
 11  \w     31.00 111.00   0.50    0.90    --   96.67-121.00 -41.00  160
 12  \w     44.00 127.00   0.50    0.90    --   96.67-145.00-120.00  166
 13  \w     29.00  68.00   0.50    0.90    --   96.67 -59.00-150.00   78
 14  \w     30.00  57.00   0.50    0.90    --   96.67 -50.00-120.00   54
 15  \w     28.00 105.00   0.50    0.90    --   96.67 -77.00 -60.00  154
 16  \w     30.00 109.00   0.50    0.90    --   96.67-117.00 -60.00  158
 17  \w     30.00  57.00   0.50    0.90    --   96.67 -50.00  90.00   54
 18  \w     29.00  68.00   0.50    0.90    --   96.67 -59.00 120.00   78
 19  \w     29.00  68.00   0.50    0.90    --   96.67 -59.00 150.00   78
 20  \w     27.00 127.00   0.50    0.90    --   96.67 -87.00 120.00  200
 21  \w     83.00 164.00   0.50    0.90    --   96.67  33.00  60.00  162
 22  \w     97.00 163.00   0.50    0.90    --   96.67 121.00  41.00  132
 23  \w     99.00 164.00   0.50    0.90    --   96.67 117.00 150.00  130
 24  \w     81.00 164.00   0.50    0.90    --   96.67 145.00   0.00  166
 25  \w    105.00 170.00   0.50    0.90    --   96.67  96.00-150.00  130
 26  \w     99.00 164.00   0.50    0.90    --   96.67 117.00-180.00  130
 27  \w     81.00 164.00   0.50    0.90    --   96.67 145.00-120.00  166
 28  \w     75.00 164.00   0.50    0.90    --   96.67  59.00 -30.00  178
 29  \w     78.00 163.00   0.50    0.90    --   96.67  50.00  90.00  170
 30  \w     83.00 164.00   0.50    0.90    --   96.67  33.00 150.00  162
 31  \w     73.00 165.00   0.50    0.90    --   96.67  68.00   0.00  184
 32  \w     75.00 164.00   0.50    0.90    --   96.67  59.00 -60.00  178
 33  \w     75.00 164.00   0.50    0.90    --   96.67 153.00-159.00  178
 34  \w     30.00  57.00   0.50    0.90    --   96.67 -50.00 120.00   54
 35  \w     22.00 106.00   0.50    0.90    --   96.67 -96.00  60.00  168
 36  \w     29.00  68.00   0.50    0.90    --   96.67 -59.00 -30.00   78
 37  \w     27.00 127.00   0.50    0.90    --   96.67 -87.00 -60.00  200
 38  \w     29.00  68.00   0.50    0.90    --   96.67 -59.00-180.00   78
 39  \w     29.00  68.00   0.50    0.90    --   96.67 -59.00 -60.00   78
 40  \w    -20.00  73.00   0.50    0.20    --   40.33 -92.00-180.00  186
 41  \w    -43.00  26.00   0.50    0.20    --  -40.33  38.00-120.00  138
 42  \w    -47.00 -15.00   0.50    0.90    --  -82.50  42.00-120.00   64
 43  \w    -47.00 -15.00   0.50    0.90    --  -82.50  42.00  30.00   64
 44  \w    -47.00 -15.00   0.50    0.90    --  -82.50  42.00  90.00   64
 45  \w    -47.00 -15.00   0.50    0.90    --  -82.50  42.00 150.00   64
 46  \w    -85.00  -9.00   0.50    0.20    --  -40.33 121.00  41.00  152
 47  \w     10.00  43.00   0.50    0.20    --   40.33  87.00 154.83   66
 48  \w     14.00 109.00   0.50    0.20    --   40.33  77.00  90.00  190
 49  \w     17.00 108.00   0.50    0.20    --   40.33  64.00 -90.00  182
 50  \w     14.00 109.00   0.50    0.20    --   40.33  77.00  30.00  190
 51  \w     14.00 109.00   0.50    0.20    --   40.33  77.00 -30.00  190
 52  \w     11.00  43.00   0.50    0.20    --   40.33  85.00 -83.76   64
 53  \w   -106.00 -26.00   0.50    0.20    --  -40.33 153.00-159.00  160
 54  \w   -106.00 -26.00   0.50    0.90    --  -82.50 153.00-159.00  160
 55  \w   -110.00 -26.00   0.50    0.20    --  -40.33 -25.00-150.00  168
 56  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00-180.00  192
 57  \w   -106.00 -25.00   0.50    0.20    --  -40.33 -38.00 -60.00  162
 58  \w   -109.00 -12.00   0.50    0.20    --  -40.33 -80.00  41.50  194
 59  \w   -109.00 -53.00   0.50    0.20    --  -40.33-153.00 159.00  112
 60  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 150.00  192
 61  \w   -107.00 -21.00   0.50    0.20    --  -40.33 -50.00  60.00  172
 62  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 -60.00  192
 63  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00-150.00  192
 64  \w   -149.00 -75.00   0.50    0.90    --  -82.50-121.00 -41.00  148
 65  \w   -149.00 -63.00   0.50    0.90    --  -82.50 -50.00 -30.00  172
 66  \w   -150.00 -66.00   0.50    0.90    --  -82.50 -42.00-150.00  168
 67  \w   -148.00 -53.00   0.50    0.90    --  -82.50-153.00 159.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0201839000
_diffrn_orient_matrix_UB_12      0.0562641000
_diffrn_orient_matrix_UB_13      0.1331789000
_diffrn_orient_matrix_UB_21      0.1194649000
_diffrn_orient_matrix_UB_22      -0.0882649000
_diffrn_orient_matrix_UB_23      -0.0005190000
_diffrn_orient_matrix_UB_31      0.1212709000
_diffrn_orient_matrix_UB_32      0.0907746000
_diffrn_orient_matrix_UB_33      -0.0142122000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0668
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20335
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        66.583
_diffrn_reflns_theta_max         66.583
_diffrn_reflns_theta_min         3.843
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.419
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76591
_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            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_description       needle
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.510
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         4263
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0451
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0777P)^2^+0.2989P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1259
_refine_ls_wR_factor_ref         0.1284
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3914
_reflns_number_total             4263
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03595b2.cif
_cod_data_source_block           kmckd-277_1
_cod_database_code               7130469
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N S O'
_chemical_oxdiff_usercomment     100K
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.920
_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
2.a Ternary CH refined with riding coordinates:
 C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11a,H11b), C9(H9a,H9b), C19(H19a,H19b)
2.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C25(H25), C13(H13), C21(H21), C27(H27), C7(H7), C18(H18), C4(H4),
 C17(H17), C14(H14), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C29(H29a,H29b,H29c), C1(H1a,H1b,H1c), C28(H28a,H28b,H28c), C16(H16a,H16b,H16c)
;
_shelx_res_checksum              27273
_shelx_hkl_checksum              58532
_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 2.146
_oxdiff_exptl_absorpt_empirical_full_min 0.638