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_1566785
_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         'C22 H30 N2 O2'
_chemical_formula_sum            'C22 H30 N2 O2'
_chemical_formula_weight         354.48
_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             2021-08-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-08-30 deposited with the CCDC.	2022-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.028(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.4831(8)
_cell_length_b                   10.8800(4)
_cell_length_c                   9.8987(3)
_cell_measurement_reflns_used    5882
_cell_measurement_temperature    302.58(10)
_cell_measurement_theta_max      73.8040
_cell_measurement_theta_min      2.3050
_cell_volume                     2072.29(13)
_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      air
_diffrn_ambient_temperature      302.58(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.955
_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     39.00  71.00   0.50    1.20    --  104.25 -61.00  30.00   64
  2  \w     93.00 168.00   0.50    1.20    --  104.25  45.00 -90.00  150
  3  \w    101.00 165.00   0.50    1.20    --  104.25  45.00-150.00  128
  4  \w    -24.00  26.00   0.50    0.50    --   46.32 -19.00-180.00  100
  5  \w     40.00  65.00   0.50    1.20    --  104.25 -77.00-180.00   50
  6  \w     70.00 106.00   0.50    1.20    --  104.25 -77.00-180.00   72
  7  \w     29.00  63.00   0.50    0.50    --   46.32-137.00-147.00   68
  8  \w     32.00 115.00   0.50    1.20    --  104.25-131.00  28.00  166
  9  \w     37.00 111.00   0.50    1.20    --  104.25-125.00  60.00  148
 10  \w     41.00  88.00   0.50    1.20    --  104.25 -94.00  90.00   94
 11  \w     25.00  96.00   0.50    0.50    --   46.32-131.00  28.00  142
 12  \w     52.00  77.00   0.50    1.20    --  104.25-137.00-147.00   50
 13  \w    -25.00  28.00   0.50    0.50    --  -46.32  19.00-120.00  106
 14  \w    -85.00 -60.00   0.50    0.50    --  -46.32 137.00 -85.00   50
 15  \w    -69.00 -31.00   0.50    1.20    -- -102.00  61.00-150.00   76
 16  \w    -81.00 -56.00   0.50    0.50    --  -46.32 131.00  98.00   50
 17  \w   -113.00 -37.00   0.50    1.20    -- -102.00 131.00  98.00  152
 18  \w    -55.00 -30.00   0.50    1.20    -- -102.00  61.00  30.00   50
 19  \w   -127.00 -86.00   0.50    1.20    -- -102.00 -61.00 -60.00   82
 20  \w   -115.00 -90.00   0.50    0.50    --  -46.32-125.00 -90.00   50
 21  \w   -114.00 -88.00   0.50    0.50    --  -46.32-137.00-147.00   52
 22  \w   -100.00 -74.00   0.50    0.50    --  -46.32-131.00  28.00   52
 23  \w   -118.00 -75.00   0.50    0.50    --  -46.32-125.00  60.00   86
 24  \w   -119.00 -74.00   0.50    0.50    --  -46.32-125.00 150.00   90
 25  \w   -173.00-140.00   0.50    1.20    -- -102.00 -61.00 -60.00   66
 26  \w   -147.00-122.00   0.50    1.20    -- -102.00-131.00  28.00   50
 27  \w   -101.00 -68.00   0.50    1.20    -- -102.00-137.00-147.00   66
;
_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      -0.0712729000
_diffrn_orient_matrix_UB_12      -0.0644394000
_diffrn_orient_matrix_UB_13      -0.0247382000
_diffrn_orient_matrix_UB_21      0.0364326000
_diffrn_orient_matrix_UB_22      -0.1260290000
_diffrn_orient_matrix_UB_23      0.0168213000
_diffrn_orient_matrix_UB_31      -0.0025268000
_diffrn_orient_matrix_UB_32      0.0033556000
_diffrn_orient_matrix_UB_33      0.1546971000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0834
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            15890
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.210
_diffrn_reflns_theta_min         2.296
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.570
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68015
_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    1.136
_exptl_crystal_description       needle
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.312
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     242
_refine_ls_number_reflns         15890
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0976
_refine_ls_R_factor_gt           0.0771
_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^)+(0.1262P)^2^+0.6353P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2360
_refine_ls_wR_factor_ref         0.2523
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11742
_reflns_number_total             15890
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00764a2.cif
_cod_data_source_block           liuhongchao_0830-1_auto
_cod_database_code               1566785
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.768(6)
 0.232(6)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B)
3.b Aromatic/amide H refined with riding coordinates:
 N3(H3), C2(H2), C3(H3A), C4(H4), C5(H5), C8(H8), C10(H10), C12(H12)
3.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              30122
_shelx_hkl_checksum              44542
_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 2.311
_oxdiff_exptl_absorpt_empirical_full_min 0.350