Ruthenium-Catalyzed Radical Cyclization/meta-Selective C–H Alkylation of Arenes via σ-Activation Strategy
Gou, Xue-Ya; Li, Yuke; Luan, Yu-Yong; Shi, Wei-Yu; Wang, Cui-Tian; An, Yang; Zhang, Bo-Sheng; Liang, Yong-Min; ACS Catalysis 11 (2021) 4263–4270; doi:10.1021/acscatal.1c00359

data_4518572
_publ_section_title
;
 Ruthenium-Catalyzed Radical Cyclization/meta-Selective C--H Alkylation of
 Arenes via \s-Activation Strategy
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              4263
_journal_page_last               4270
_journal_paper_doi               10.1021/acscatal.1c00359
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C25 H27 N3 O3'
_chemical_formula_sum            'C25 H27 N3 O3'
_chemical_formula_weight         417.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-25
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.248(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.7124(14)
_cell_length_b                   6.29804(19)
_cell_length_c                   22.6491(5)
_cell_measurement_reflns_used    5762
_cell_measurement_temperature    285.3(4)
_cell_measurement_theta_max      74.5590
_cell_measurement_theta_min      2.6880
_cell_volume                     4516.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      285.3(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.919
_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    -27.00   1.00   1.00    0.20    --  -43.05  51.00  10.00   28
  2  \w    -51.00 -24.00   1.00    0.80    -- -100.00  45.00 120.00   27
  3  \w    -54.00 -25.00   1.00    0.80    -- -100.00  45.00 150.00   29
  4  \w    -53.00 -26.00   1.00    0.80    -- -100.00  45.00  90.00   27
  5  \w    -61.00 -27.00   1.00    0.80    -- -100.00  51.00  10.00   34
  6  \w    -54.00 -24.00   1.00    0.80    -- -100.00  45.00 -30.00   30
  7  \w    -66.00 -26.00   1.00    0.80    -- -100.00  61.00  30.00   40
  8  \w    -64.00 -36.00   1.00    0.80    -- -100.00  77.00  90.00   28
  9  \w   -118.00 -79.00   1.00    0.80    -- -100.00 -45.00 150.00   39
 10  \w   -169.00-120.00   1.00    0.80    -- -100.00 -45.00 150.00   49
 11  \w   -170.00-118.00   1.00    0.80    -- -100.00 -61.00 -60.00   52
 12  \w   -111.00 -76.00   1.00    0.80    -- -100.00 -61.00 -60.00   35
 13  \w    -97.00 -24.00   1.00    0.20    --  -43.05 -51.00-134.00   73
 14  \w    -53.00 -26.00   1.00    0.80    -- -100.00  45.00-120.00   27
 15  \w    -53.00 -25.00   1.00    0.80    -- -100.00  45.00-150.00   28
 16  \w    -51.00 -24.00   1.00    0.80    -- -100.00  45.00-180.00   27
 17  \w    -73.00 -45.00   1.00    0.80    -- -100.00  61.00-180.00   28
 18  \w   -172.00 -78.00   1.00    0.80    -- -100.00 -51.00-134.00   94
 19  \w     -7.00  21.00   1.00    0.20    --   43.05 -51.00-134.00   28
 20  \w    -36.00  25.00   1.00    0.20    --   43.05 -19.00 -90.00   61
 21  \w     28.00 116.00   1.00    0.20    --   43.05  51.00  10.00   88
 22  \w     93.00 121.00   1.00    0.80    --  109.26  51.00  10.00   28
 23  \w    142.00 169.00   1.00    0.80    --  109.26  30.00 -60.00   27
 24  \w    107.00 135.00   1.00    0.80    --  109.26  30.00 -60.00   28
 25  \w     40.00  67.00   1.00    0.80    --  109.26 -61.00  90.00   27
 26  \w     35.00  62.00   1.00    0.80    --  109.26 -61.00 120.00   27
 27  \w     35.00  62.00   1.00    0.80    --  109.26 -61.00  60.00   27
 28  \w     37.00  69.00   1.00    0.80    --  109.26 -61.00-120.00   32
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0196650000
_diffrn_orient_matrix_UB_12      0.0723252000
_diffrn_orient_matrix_UB_13      -0.0572817000
_diffrn_orient_matrix_UB_21      0.0395265000
_diffrn_orient_matrix_UB_22      -0.1347562000
_diffrn_orient_matrix_UB_23      0.0160928000
_diffrn_orient_matrix_UB_31      -0.0204212000
_diffrn_orient_matrix_UB_32      -0.1909894000
_diffrn_orient_matrix_UB_33      -0.0331920000
_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  0.0312
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.919
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            13806
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.774
_diffrn_reflns_theta_min         2.791
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32792
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.228
_exptl_crystal_description       block
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.195
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.00053(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         4316
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0650
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0780P)^2^+1.8870P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1483
_refine_ls_wR_factor_ref         0.1555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3594
_reflns_number_total             4316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00359_si_003.cif
_cod_data_source_block           gouxy_1225_1
_cod_depositor_comments
'Adding full bibliography for 4518571--4518573.cif.'
_cod_original_cell_volume        4516.4(3)
_cod_database_code               4518572
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.962
_reflns_odcompleteness_completeness 97.84
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C18(H18), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              21207
_shelx_hkl_checksum              27729
_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 2.529
_oxdiff_exptl_absorpt_empirical_full_min 0.596