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_1566783
_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         'C26 H35 N5 O2'
_chemical_formula_sum            'C26 H35 N5 O2'
_chemical_formula_weight         449.59
_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             2021-07-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-08-03 deposited with the CCDC.	2022-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.265(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3083(3)
_cell_length_b                   24.7520(7)
_cell_length_c                   10.4153(4)
_cell_measurement_reflns_used    6631
_cell_measurement_temperature    303.04(10)
_cell_measurement_theta_max      75.3820
_cell_measurement_theta_min      1.7860
_cell_volume                     2523.58(15)
_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      303.04(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 0.965
_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    114.00 175.00   0.50    1.00    --  104.25  45.00 -60.00  122
  2  \w     94.00 174.00   0.50    1.00    --  104.25  22.00  73.00  160
  3  \w     50.00 121.00   0.50    0.20    --   46.32  22.00  73.00  142
  4  \w   -115.00 -90.00   0.50    0.20    --  -46.32-125.00  90.00   50
  5  \w   -111.00 -81.00   0.50    0.20    --  -46.32-175.00  40.00   60
  6  \w    -69.00 -44.00   0.50    0.20    --  -46.32-175.00  40.00   50
  7  \w    -91.00 -57.00   0.50    1.00    -- -102.00 114.00 -89.00   68
  8  \w    -25.00  29.00   0.50    0.20    --  -46.32  19.00-180.00  108
  9  \w     32.00 103.00   0.50    1.00    --  104.25-125.00-120.00  142
 10  \w     42.00  68.00   0.50    1.00    --  104.25-108.00  83.00   52
 11  \w     34.00  95.00   0.50    1.00    --  104.25 -94.00 120.00  122
 12  \w     33.00  62.00   0.50    1.00    --  104.25 -61.00  60.00   58
 13  \w    -79.00 -29.00   0.50    0.20    -- -102.00 103.00-120.00  100
 14  \w   -110.00 -84.00   0.50    0.20    --  -46.32-125.00-180.00   52
 15  \w   -115.00 -85.00   0.50    0.20    --  -46.32-125.00 -90.00   60
 16  \w   -119.00 -94.00   0.50    0.20    --  -46.32-125.00  30.00   50
 17  \w     -6.00  29.00   0.50    0.20    --   46.32 -19.00 -60.00   70
 18  \w    -19.00  19.00   0.50    0.20    --   46.32 -19.00-120.00   76
 19  \w    -69.00 -29.00   0.50    0.20    -- -102.00  61.00   0.00   80
 20  \w    -63.00 -31.00   0.50    0.20    -- -102.00  61.00  30.00   64
 21  \w    -69.00 -44.00   0.50    0.20    -- -102.00  61.00 -90.00   50
 22  \w    -68.00 -42.00   0.50    0.20    -- -102.00  61.00  60.00   52
 23  \w    137.00 166.00   0.50    0.20    --  104.25  77.00 150.00   58
 24  \w     89.00 126.00   0.50    0.20    --  104.25  77.00 150.00   74
 25  \w    137.00 163.00   0.50    0.20    --  104.25  30.00 -90.00   52
 26  \w     39.00  64.00   0.50    0.20    --  104.25 -61.00   0.00   50
 27  \w     43.00  98.00   0.50    0.20    --  104.25 -94.00 150.00  110
 28  \w     40.00  65.00   0.50    0.20    --  104.25 -61.00 150.00   50
 29  \w     44.00  70.00   0.50    0.20    --  104.25 -61.00-180.00   52
 30  \w     36.00  63.00   0.50    0.20    --  104.25 -61.00 -90.00   54
;
_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      0.0200522000
_diffrn_orient_matrix_UB_12      0.0172238000
_diffrn_orient_matrix_UB_13      0.1471070000
_diffrn_orient_matrix_UB_21      -0.1557050000
_diffrn_orient_matrix_UB_22      -0.0019864000
_diffrn_orient_matrix_UB_23      -0.0273808000
_diffrn_orient_matrix_UB_31      0.0108550000
_diffrn_orient_matrix_UB_32      -0.0597865000
_diffrn_orient_matrix_UB_33      0.0432208000
_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  0.0428
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19037
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.252
_diffrn_reflns_theta_min         3.571
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.608
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90035
_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    1.183
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.344
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.034
_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     321
_refine_ls_number_reflns         5099
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0830
_refine_ls_R_factor_gt           0.0625
_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^)+(0.1021P)^2^+0.3891P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1861
_refine_ls_wR_factor_ref         0.2029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3610
_reflns_number_total             5099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00764a2.cif
_cod_data_source_block           liuhonghao_0726_auto
_cod_original_cell_volume        2523.58(16)
_cod_database_code               1566783
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 99.74
_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. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq, Uanis(C00O) \\sim Ueq, Uanis(C00M) \\sim Ueq, Uanis(C1)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: C00M(0.8) H00A(0.8) H00C(0.8) C00O(0.8) H00D(0.8) H00E(0.8)
 C1(0.2) H1A(0.2) H1B(0.2) C2(0.2) H2A(0.2) H2B(0.2)
4.a Ternary CH refined with riding coordinates:
 C00H(H00H)
4.b Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00C), C00O(H00D,H00E), C00S(H00U,H00V), C00T(H00W,H00X), C00U(H00Y,
 H), C00X(H1,HE), C1(H1A,H1B), C2(H2A,H2B)
4.c Aromatic/amide H refined with riding coordinates:
 N004(H004), C00B(H00B), C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L),
 C00N(H00N)
4.d Idealised Me refined as rotating group:
 C00P(H00F,H00G,H00M), C00Q(H00O,H00P,H00Q), C00R(H00R,H00S,H00T), C00V(H00Z,
 HA,HB), C00W(H00,HC,HD)
;
_shelx_res_checksum              67302
_shelx_hkl_checksum              20070
_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 2.047
_oxdiff_exptl_absorpt_empirical_full_min 0.636