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_4518571
_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         'C27 H30 N4 O3'
_chemical_formula_sum            'C27 H30 N4 O3'
_chemical_formula_weight         458.55
_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     direct
_audit_creation_date             2021-01-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_cell_angle_alpha                82.853(13)
_cell_angle_beta                 85.165(12)
_cell_angle_gamma                89.890(12)
_cell_formula_units_Z            2
_cell_length_a                   5.8360(7)
_cell_length_b                   10.2615(16)
_cell_length_c                   21.051(3)
_cell_measurement_reflns_used    2273
_cell_measurement_temperature    291.51(10)
_cell_measurement_theta_max      68.6120
_cell_measurement_theta_min      2.1170
_cell_volume                     1246.4(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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.51(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.928
_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     33.00  81.00   1.00    0.50    --   43.05  28.00  -3.00   48
  2  \w     97.00 122.00   1.00    0.50    --   43.05  28.00  -3.00   25
  3  \w    110.00 175.00   1.00    2.00    --  109.26  28.00  -3.00   65
  4  \w     81.00 119.00   1.00    0.50    --   43.05 179.00 -30.00   38
  5  \w     76.00 163.00   1.00    2.00    --  109.26 125.00 -90.00   87
  6  \w     42.00  78.00   1.00    0.50    --   43.05 179.00 -30.00   36
  7  \w    -36.00  36.00   1.00    0.50    --  -43.05  28.00  -3.00   72
  8  \w    -36.00  18.00   1.00    0.50    --   43.05 -28.00-164.00   54
  9  \w     72.00 111.00   1.00    2.00    --  109.26-125.00 -90.00   39
 10  \w     72.00 105.00   1.00    2.00    --  109.26 -94.00 -60.00   33
 11  \w     36.00  68.00   1.00    2.00    --  109.26 -61.00   0.00   32
 12  \w     40.00  66.00   1.00    2.00    --  109.26 -61.00 -30.00   26
 13  \w     39.00  97.00   1.00    2.00    --  109.26 -94.00-180.00   58
 14  \w    -61.00 -18.00   1.00    0.50    --  -43.05 -28.00-164.00   43
 15  \w    -32.00  27.00   1.00    0.50    --   43.05 -37.00 150.00   59
 16  \w     84.00 110.00   1.00    2.00    --  109.26-125.00 150.00   26
 17  \w     56.00 120.00   1.00    0.50    --   43.05-179.00 150.00   64
 18  \w    -50.00 -25.00   1.00    2.00    -- -100.00  45.00-150.00   25
 19  \w    -70.00 -37.00   1.00    2.00    -- -100.00 139.00-136.58   33
 20  \w    -53.00 -24.00   1.00    2.00    -- -100.00  45.00   0.00   29
 21  \w    -54.00 -24.00   1.00    2.00    -- -100.00  45.00  60.00   30
 22  \w    -53.00 -24.00   1.00    2.00    -- -100.00  45.00 120.00   29
 23  \w    -54.00 -29.00   1.00    2.00    -- -100.00  45.00 150.00   25
 24  \w    -63.00 -35.00   1.00    2.00    -- -100.00  61.00 120.00   28
 25  \w    -74.00 -41.00   1.00    2.00    -- -100.00  61.00  60.00   33
 26  \w    -56.00 -26.00   1.00    2.00    -- -100.00  61.00   0.00   30
 27  \w   -104.00 -52.00   1.00    2.00    -- -100.00 125.00 -90.00   52
 28  \w   -122.00 -93.00   1.00    2.00    -- -100.00 139.00-136.58   29
 29  \w   -112.00 -76.00   1.00    2.00    -- -100.00 125.00   0.00   36
 30  \w   -102.00 -44.00   1.00    2.00    -- -100.00 125.00  30.00   58
 31  \w   -112.00 -81.00   1.00    2.00    -- -100.00 125.00 150.00   31
 32  \w   -170.00-119.00   1.00    2.00    -- -100.00 -28.00-164.00   51
 33  \w   -166.00 -83.00   1.00    2.00    -- -100.00-125.00   0.00   83
 34  \w   -118.00 -88.00   1.00    2.00    -- -100.00 -94.00  90.00   30
 35  \w   -146.00 -90.00   1.00    2.00    -- -100.00-125.00 120.00   56
 36  \w   -157.00 -82.00   1.00    2.00    -- -100.00-125.00 150.00   75
 37  \w   -174.00-121.00   1.00    2.00    -- -100.00 -94.00  90.00   53
;
_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      0.2565290000
_diffrn_orient_matrix_UB_12      0.0375337000
_diffrn_orient_matrix_UB_13      -0.0025989000
_diffrn_orient_matrix_UB_21      -0.0653583000
_diffrn_orient_matrix_UB_22      0.1274561000
_diffrn_orient_matrix_UB_23      0.0285508000
_diffrn_orient_matrix_UB_31      0.0125606000
_diffrn_orient_matrix_UB_32      -0.0724464000
_diffrn_orient_matrix_UB_33      0.0681701000
_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  0.0538
_diffrn_reflns_av_unetI/netI     0.0742
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            11995
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.843
_diffrn_reflns_theta_min         2.123
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.650
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45459
_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    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.172
_refine_diff_density_min         -0.142
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     330
_refine_ls_number_reflns         4811
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.1103
_refine_ls_R_factor_gt           0.0723
_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^)+(0.0725P)^2^+0.1652P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1730
_refine_ls_wR_factor_ref         0.1947
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3211
_reflns_number_total             4811
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00359_si_002.cif
_cod_data_source_block           gouxy_1004
_cod_depositor_comments
'Adding full bibliography for 4518571--4518573.cif.'
_cod_database_code               4518571
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.974
_reflns_odcompleteness_completeness 99.53
_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(C26B) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C27B)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: C26(0.6) H26A(0.6) H26B(0.6) C27(0.6) H27A(0.6) H27B(0.6)
 H27C(0.6) C26B(0.4) H26C(0.4) H26D(0.4) C27B(0.4) H27D(0.4) H27E(0.4) H27F(0.4)
4.a Ternary CH refined with riding coordinates:
 C12(H12), C13(H13)
4.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C26(H26A,H26B), C26B(H26C,H26D)
4.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C10(H10), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C27(H27A,H27B,
 H27C), C27B(H27D,H27E,H27F)
;
_shelx_res_checksum              16820
_shelx_hkl_checksum              91119
_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 4.338
_oxdiff_exptl_absorpt_empirical_full_min 0.493