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_7130470
_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         'C32 H29 N O3 S'
_chemical_formula_sum            'C32 H29 N O3 S'
_chemical_formula_weight         507.62
_chemical_name_systematic        'KMC KD 273'
_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                74.3850(10)
_cell_angle_beta                 86.4320(10)
_cell_angle_gamma                89.0320(10)
_cell_formula_units_Z            2
_cell_length_a                   9.92120(10)
_cell_length_b                   10.49310(10)
_cell_length_c                   12.89360(10)
_cell_measurement_reflns_used    16358
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      66.3990
_cell_measurement_theta_min      3.5580
_cell_volume                     1290.23(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 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      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_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     13.00 109.00   0.50    0.20    --   40.33  79.00   6.11  192
  2  \w     78.00 163.00   0.50    0.45    --   96.67  50.00  90.00  170
  3  \w     83.00 164.00   0.50    0.45    --   96.67  33.00 150.00  162
  4  \w     73.00 165.00   0.50    0.45    --   96.67  68.00   0.00  184
  5  \w     14.00 109.00   0.50    0.20    --   40.33  77.00-120.00  190
  6  \w     83.00 164.00   0.50    0.45    --   96.67  33.00-180.00  162
  7  \w     71.00 170.00   0.50    0.45    --   96.67  17.00-120.00  198
  8  \w     82.00 167.00   0.50    0.45    --   96.67  25.00 -60.00  170
  9  \w     70.00 165.00   0.50    0.45    --   96.67  77.00 -60.00  190
 10  \w     83.00 164.00   0.50    0.45    --   96.67  33.00  60.00  162
 11  \w    -26.00  43.00   0.50    0.20    --   40.33 -38.00  60.00  138
 12  \w    -30.00  31.00   0.50    0.20    --   40.33 -25.00   0.00  122
 13  \w    -35.00  24.00   0.50    0.20    --   40.33 -12.00 -60.00  118
 14  \w    -35.00  24.00   0.50    0.20    --   40.33 -12.00-150.00  118
 15  \w     27.00 127.00   0.50    0.45    --   96.67 -87.00-150.00  200
 16  \w     41.00 100.00   0.50    0.20    --   40.33-139.00 -21.00  118
 17  \w     41.00 122.00   0.50    0.45    --   96.67-139.00 -21.00  162
 18  \w     30.00 109.00   0.50    0.45    --   96.67-117.00-150.00  158
 19  \w     30.00 109.00   0.50    0.45    --   96.67-117.00   0.00  158
 20  \w     44.00 127.00   0.50    0.45    --   96.67-145.00  90.00  166
 21  \w     37.00 117.00   0.50    0.45    --   96.67-131.00 152.00  160
 22  \w     37.00  95.00   0.50    0.20    --   40.33-131.00 152.00  116
 23  \w     22.00 106.00   0.50    0.45    --   96.67 -96.00 150.00  168
 24  \w     22.00 106.00   0.50    0.45    --   96.67 -96.00  90.00  168
 25  \w     22.00 106.00   0.50    0.45    --   96.67 -96.00   0.00  168
 26  \w     22.00 106.00   0.50    0.45    --   96.67 -96.00 -90.00  168
 27  \w     28.00 105.00   0.50    0.45    --   96.67 -77.00 -30.00  154
 28  \w     29.00  68.00   0.50    0.45    --   96.67 -59.00  90.00   78
 29  \w     29.00  83.00   0.50    0.45    --   96.67 -68.00 120.00  108
 30  \w     29.00  68.00   0.50    0.45    --   96.67 -59.00 150.00   78
 31  \w     29.00  83.00   0.50    0.45    --   96.67 -68.00  90.00  108
 32  \w     29.00  83.00   0.50    0.45    --   96.67 -68.00  30.00  108
 33  \w     29.00  68.00   0.50    0.45    --   96.67 -59.00   0.00   78
 34  \w     30.00  57.00   0.50    0.45    --   96.67 -50.00  30.00   54
 35  \w     30.00  57.00   0.50    0.45    --   96.67 -50.00 -30.00   54
 36  \w     30.00  57.00   0.50    0.45    --   96.67 -50.00 -90.00   54
 37  \w     30.00  57.00   0.50    0.45    --   96.67 -50.00-120.00   54
 38  \w     29.00  68.00   0.50    0.45    --   96.67 -59.00-150.00   78
 39  \w     29.00  68.00   0.50    0.45    --   96.67 -59.00-180.00   78
 40  \w     11.00  43.00   0.50    0.20    --   40.33  85.00  96.34   64
 41  \w      7.00  35.00   0.50    0.20    --   40.33  94.00  68.82   56
 42  \w     10.00  43.00   0.50    0.20    --   40.33  87.00 -53.39   66
 43  \w     91.00 163.00   0.50    0.45    --   96.67 131.00-136.00  144
 44  \w     85.00 164.00   0.50    0.45    --   96.67 139.00  38.00  158
 45  \w   -106.00 -25.00   0.50    0.20    --  -40.33 -38.00   0.00  162
 46  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 150.00  192
 47  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 120.00  192
 48  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00  90.00  192
 49  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00  30.00  192
 50  \w   -107.00 -21.00   0.50    0.20    --  -40.33 -50.00 -90.00  172
 51  \w   -107.00 -21.00   0.50    0.20    --  -40.33 -50.00 -60.00  172
 52  \w   -106.00 -25.00   0.50    0.20    --  -40.33 -38.00 120.00  162
 53  \w   -109.00 -13.00   0.50    0.20    --  -40.33 -77.00 -90.00  192
 54  \w   -109.00 -14.00   0.50    0.20    --  -40.33 -76.00-171.57  190
 55  \w   -107.00 -21.00   0.50    0.20    --  -40.33 -50.00-180.00  172
 56  \w   -153.00 -78.00   0.50    0.45    --  -82.50 -87.00 -90.00  150
 57  \w   -151.00 -56.00   0.50    0.45    --  -82.50 -74.00-136.88  190
 58  \w   -151.00 -63.00   0.50    0.45    --  -82.50-139.00 -21.00  176
 59  \w   -150.00 -69.00   0.50    0.45    --  -82.50-131.00 152.00  162
 60  \w   -151.00 -55.00   0.50    0.45    --  -82.50 -77.00  33.95  192
 61  \w   -149.00 -63.00   0.50    0.45    --  -82.50 -50.00 -30.00  172
 62  \w    -68.00 -14.00   0.50    0.45    --  -82.50  59.00-150.00  108
 63  \w    -31.00  30.00   0.50    0.20    --  -40.33  25.00-120.00  122
 64  \w    -57.00  26.00   0.50    0.20    --  -40.33  50.00 -90.00  166
 65  \w    -57.00 -16.00   0.50    0.45    --  -82.50  50.00 -60.00   82
 66  \w    -57.00 -16.00   0.50    0.45    --  -82.50  50.00  30.00   82
 67  \w    -97.00 -20.00   0.50    0.20    --  -40.33 139.00  38.00  154
 68  \w    -91.00 -15.00   0.50    0.20    --  -40.33 131.00-136.00  152
 69  \w    -91.00 -15.00   0.50    0.45    --  -82.50 131.00-136.00  152
;
_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      0.0135030000
_diffrn_orient_matrix_UB_12      -0.0491839000
_diffrn_orient_matrix_UB_13      0.1227447000
_diffrn_orient_matrix_UB_21      -0.1290278000
_diffrn_orient_matrix_UB_22      0.0763644000
_diffrn_orient_matrix_UB_23      0.0190571000
_diffrn_orient_matrix_UB_31      -0.0858783000
_diffrn_orient_matrix_UB_32      -0.1224262000
_diffrn_orient_matrix_UB_33      0.0041553000
_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  0.0505
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            22997
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        66.587
_diffrn_reflns_theta_max         66.587
_diffrn_reflns_theta_min         3.566
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.387
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84672
_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 grayish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   grayish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_description       plate
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.083
_refine_diff_density_min         -0.680
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         4508
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0585
_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^)+(0.0513P)^2^+2.5835P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1387
_refine_ls_wR_factor_ref         0.1396
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4358
_reflns_number_total             4508
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03595b2.cif
_cod_data_source_block           kmc-kd-273_1
_cod_database_code               7130470
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     100K
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.921
_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:
 C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14a,H14b), C24(H24a,H24b), C16(H16a,H16b)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C1(H1), C4(H4), C23(H23), C28(H28), C22(H22), C3(H3), C19(H19),
 C11(H11), C9(H9), C2(H2), C18(H18), C12(H12), C10(H10), C32(H32), C29(H29),
 C26(H26), C31(H31), C30(H30)
2.d Idealised Me refined as rotating group:
 C21(H21a,H21b,H21c)
;
_shelx_res_checksum              8326
_shelx_hkl_checksum              17067
_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 1.662
_oxdiff_exptl_absorpt_empirical_full_min 0.721