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_4518573
_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 H28 N2 O4'
_chemical_formula_sum            'C25 H28 N2 O4'
_chemical_formula_weight         420.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-28
_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                 91.726(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4070(5)
_cell_length_b                   11.0997(12)
_cell_length_c                   31.594(4)
_cell_measurement_reflns_used    2978
_cell_measurement_temperature    287(1)
_cell_measurement_theta_max      66.4220
_cell_measurement_theta_min      2.8040
_cell_volume                     2245.8(4)
_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      287(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.921
_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    -34.00  26.00   1.00    1.00    --   43.05 -19.00   0.00   60
  2  \w    -37.00  23.00   1.00    1.00    --   43.05 -19.00 -60.00   60
  3  \w     66.00  96.00   1.00    3.50    --  109.26 -94.00 -60.00   30
  4  \w     38.00 108.00   1.00    3.50    --  109.26 -77.00 -30.00   70
  5  \w     54.00  84.00   1.00    1.00    --   43.05-138.00 127.00   30
  6  \w     36.00  86.00   1.00    3.50    --  109.26-138.00 127.00   50
  7  \w     81.00 121.00   1.00    3.50    --  109.26-138.00 127.00   40
  8  \w     66.00  96.00   1.00    3.50    --  109.26 -94.00 150.00   30
  9  \w     21.00  91.00   1.00    1.00    --   43.05-131.00 -57.00   70
 10  \w    -19.00  31.00   1.00    1.00    --  -43.05  19.00 -90.00   50
 11  \w    -53.00 -33.00   1.00    3.50    -- -100.00  45.00-180.00   20
 12  \w    -54.00 -24.00   1.00    3.50    -- -100.00  45.00-120.00   30
 13  \w    -54.00 -24.00   1.00    3.50    -- -100.00  45.00 -60.00   30
 14  \w    -70.00 -30.00   1.00    3.50    -- -100.00  61.00-120.00   40
 15  \w    -54.00 -24.00   1.00    3.50    -- -100.00  45.00-150.00   30
 16  \w    -91.00 -61.00   1.00    1.00    --  -43.05 138.00-170.00   30
 17  \w   -117.00 -37.00   1.00    3.50    -- -100.00 138.00-170.00   80
 18  \w     68.00 108.00   1.00    1.00    --   43.05 138.00-170.00   40
 19  \w     92.00 122.00   1.00    3.50    --  109.26  45.00 120.00   30
 20  \w    126.00 166.00   1.00    3.50    --  109.26  45.00 120.00   40
 21  \w     99.00 129.00   1.00    3.50    --  109.26 131.00  13.00   30
 22  \w    -54.00 -24.00   1.00    3.50    -- -100.00  45.00 120.00   30
 23  \w    -54.00 -24.00   1.00    3.50    -- -100.00  45.00 150.00   30
 24  \w   -148.00-118.00   1.00    3.50    -- -100.00-138.00 127.00   30
 25  \w   -112.00 -82.00   1.00    3.50    -- -100.00-125.00  90.00   30
;
_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      0.0089937000
_diffrn_orient_matrix_UB_12      -0.1295650000
_diffrn_orient_matrix_UB_13      -0.0172585000
_diffrn_orient_matrix_UB_21      0.0019284000
_diffrn_orient_matrix_UB_22      0.0493603000
_diffrn_orient_matrix_UB_23      -0.0455491000
_diffrn_orient_matrix_UB_31      0.2405578000
_diffrn_orient_matrix_UB_32      0.0046423000
_diffrn_orient_matrix_UB_33      0.0024596000
_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  0.0463
_diffrn_reflns_av_unetI/netI     0.0615
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.921
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            12770
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.836
_diffrn_reflns_theta_min         2.799
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.682
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63334
_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    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.186
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.0013(3)
_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   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         4286
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1099
_refine_ls_R_factor_gt           0.0693
_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^)+(0.0854P)^2^+0.4506P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1752
_refine_ls_wR_factor_ref         0.2085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2683
_reflns_number_total             4286
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00359_si_004.cif
_cod_data_source_block           gouxy_1225_2_2
_cod_depositor_comments
'Adding full bibliography for 4518571--4518573.cif.'
_cod_database_code               4518573
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.973
_reflns_odcompleteness_completeness 97.51
_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:
 C8(H8), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C21(H21A,H21B), C22(H22A,H22B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C15(H15), C17(H17), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              56257
_shelx_hkl_checksum              32889
_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 2.892
_oxdiff_exptl_absorpt_empirical_full_min 0.610