Site-Selective Coupling of Remote C(sp3)−H/meta-C(sp2)−H Bonds Enabled by Ru/Photoredox Dual Catalysis and Mechanistic Studies
Liu, Hong-Chao; Kong, Xiangtao; Gong, Xiao-Ping; Li, Yuke; Niu, Zhi-Jie; Gou, Xue-Ya; Li, Xue-Song; Wang, Yu-Zhao; Shi, Wei-Yu; Huang, Yan-Chong; Liu, Xue-Yuan; Liang, Yong-Min; Chemical Science  (2022) –; doi:10.1039/D2SC00764A

data_1566784
_publ_section_title
;
 Site-Selective Coupling of Remote C(sp3)&#x2212;H/meta-C(sp2)&#x2212;H
 Bonds Enabled by Ru/Photoredox Dual Catalysis and Mechanistic Studies
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00764A
_journal_year                    2022
_chemical_formula_moiety         'C20 H26 Br N3 O'
_chemical_formula_sum            'C20 H26 Br N3 O'
_chemical_formula_weight         404.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-08-26 deposited with the CCDC.	2022-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.3165(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.36816(5)
_cell_length_b                   31.0073(3)
_cell_length_c                   10.01092(9)
_cell_measurement_reflns_used    10668
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.1290
_cell_measurement_theta_min      4.6600
_cell_volume                     1960.66(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.948
_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     54.00  79.00   0.50    0.05    --   46.32  61.00 -91.00   50
  2  \w    104.00 164.00   0.50    0.05    --  104.25  61.00-180.00  120
  3  \w     88.00 174.00   0.50    0.05    --  104.25  61.00 -91.00  172
  4  \w     97.00 152.00   0.50    0.05    --  104.25  45.00 -30.00  110
  5  \w     32.00 102.00   0.50    0.05    --  104.25 -77.00 -90.00  140
  6  \w     32.00  59.00   0.50    0.05    --  104.25 -61.00-150.00   54
  7  \w     40.00  73.00   0.50    0.05    --  104.25 -61.00 -30.00   66
  8  \w     32.00  57.00   0.50    0.05    --  104.25 -61.00 129.00   50
  9  \w    -25.00  48.00   0.50    0.05    --   46.32 -61.00 129.00  146
 10  \w    -63.00  25.00   0.50    0.05    --  -46.32  61.00 -91.00  176
 11  \w    -68.00 -32.00   0.50    0.05    -- -102.00  61.00-120.00   72
 12  \w    -63.00 -38.00   0.50    0.05    -- -102.00  61.00 -91.00   50
 13  \w    -68.00 -38.00   0.50    0.05    -- -102.00  61.00  30.00   60
 14  \w    -91.00 -30.00   0.50    0.05    -- -102.00 125.00 120.00  122
 15  \w     33.00 111.00   0.50    0.05    --  104.25-125.00 120.00  156
 16  \w   -154.00-129.00   0.50    0.05    -- -102.00 -61.00 129.00   50
 17  \w   -175.00-137.00   0.50    0.05    -- -102.00 -94.00  60.00   76
 18  \w   -129.00 -87.00   0.50    0.05    -- -102.00 -94.00  60.00   84
 19  \w   -106.00 -56.00   0.50    0.05    --  -46.32 -61.00 129.00  100
 20  \w    -84.00 -74.00   0.50    0.05    --  -46.32-125.00 -90.00   20
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1724598000
_diffrn_orient_matrix_UB_12      -0.0338315000
_diffrn_orient_matrix_UB_13      0.0154983000
_diffrn_orient_matrix_UB_21      -0.0105282000
_diffrn_orient_matrix_UB_22      -0.0113671000
_diffrn_orient_matrix_UB_23      -0.1505002000
_diffrn_orient_matrix_UB_31      0.1721716000
_diffrn_orient_matrix_UB_32      -0.0345656000
_diffrn_orient_matrix_UB_33      0.0343199000
_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  0.0243
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            12690
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.447
_diffrn_reflns_theta_min         4.676
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.946
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53016
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.052
_refine_ls_extinction_coef       0.00261(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         3894
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0272
_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^)+(0.0261P)^2^+1.1912P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0656
_refine_ls_wR_factor_ref         0.0663
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3729
_reflns_number_total             3894
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00764a2.cif
_cod_data_source_block           liuhch_0824_auto
_cod_original_cell_volume        1960.65(3)
_cod_database_code               1566784
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 98.44
_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 Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 N3(H3), C2(H2), C4(H4), C6(H6), C7(H7), C8(H8), C10(H10)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              61436
_shelx_hkl_checksum              28270
_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 1.687
_oxdiff_exptl_absorpt_empirical_full_min 0.567