Ruthenium-catalyzed cascade C-H activation/annulation of N-alkoxybenzamides: reaction development and mechanistic insight
Song, Liangliang; Zhang, Xiaoyong; Tang, Xiao; Van Meervelt, Luc; Van der Eycken, Johan; Harvey, Jeremy; Van der Eycken, Erik V.; Chemical Science  (2020) –; doi:10.1039/D0SC04434B

data_1559214
_publ_section_title
;
 Ruthenium-catalyzed cascade C-H activation/annulation of
 N-alkoxybenzamides: reaction development and mechanistic insight
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04434B
_journal_year                    2020
_chemical_formula_moiety         'C20 H21 N O3, C H2 Cl2'
_chemical_formula_sum            'C21 H23 Cl2 N O3'
_chemical_formula_weight         408.30
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-17 deposited with the CCDC.	2020-09-28 downloaded from the CCDC.
;
_cell_angle_alpha                82.687(4)
_cell_angle_beta                 71.563(4)
_cell_angle_gamma                87.665(4)
_cell_formula_units_Z            2
_cell_length_a                   8.9486(5)
_cell_length_b                   9.5948(4)
_cell_length_c                   12.8823(6)
_cell_measurement_reflns_used    8065
_cell_measurement_temperature    293
_cell_measurement_theta_max      28.1090
_cell_measurement_theta_min      2.5020
_cell_volume                     1040.77(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9631
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_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    -20.00  25.00   1.00   20.00    --  -17.15 -99.00-150.00   45
  2  \w    -93.00 -35.00   1.00   20.00    --  -17.15-178.00   0.00   58
  3  \w    -20.00  25.00   1.00   20.00    --  -17.15 -99.00  60.00   45
  4  \w     -7.00  91.00   1.00   20.00    --   18.79  38.00  60.00   98
  5  \w     35.00  95.00   1.00   20.00    --   18.79 178.00 -90.00   60
  6  \w    -50.00  39.00   1.00   20.00    --   18.79 -57.00 -60.00   89
  7  \w    -54.00  44.00   1.00   20.00    --   18.79 -38.00-120.00   98
  8  \w    -20.00  25.00   1.00   20.00    --  -17.15 -99.00 -90.00   45
  9  \w    -20.00  25.00   1.00   20.00    --  -17.15 -99.00 120.00   45
 10  \w    -20.00  61.00   1.00   20.00    --   18.79 -99.00  90.00   81
 11  \w     -3.00  88.00   1.00   20.00    --   18.79  57.00 -30.00   91
 12  \w    -20.00  61.00   1.00   20.00    --   18.79 -99.00-120.00   81
 13  \w    -25.00  92.00   1.00   20.00    --   18.79  19.00 -60.00  117
 14  \w     -3.00  84.00   1.00   20.00    --   18.79  57.00 150.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0547241000
_diffrn_orient_matrix_UB_12      -0.0285693000
_diffrn_orient_matrix_UB_13      0.0505762000
_diffrn_orient_matrix_UB_21      0.0630556000
_diffrn_orient_matrix_UB_22      -0.0280369000
_diffrn_orient_matrix_UB_23      0.0184173000
_diffrn_orient_matrix_UB_31      0.0032010000
_diffrn_orient_matrix_UB_32      0.0628709000
_diffrn_orient_matrix_UB_33      0.0228294000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0220
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21373
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.399
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.332
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77630
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       block
_exptl_crystal_F_000             428
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         4239
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0866
_refine_ls_R_factor_gt           0.0650
_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^)+(0.0766P)^2^+0.5873P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1713
_refine_ls_wR_factor_ref         0.1897
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3015
_reflns_number_total             4239
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04434b2.cif
_cod_data_source_block           ev2029
_cod_database_code               1559214
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C20 H21 N1 O3'
_chemical_oxdiff_usercomment     SLL-2
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C25(H25A,H25B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
2.d Idealised tetrahedral OH refined as rotating group with stretchable bonds:
 O18(H18)
;
_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 1.343
_oxdiff_exptl_absorpt_empirical_full_min 0.570