Selective C(sp3)–H Bond Insertion in Carbene/Alkyne Metathesis Reactions. Enantioselective Construction of Dihydroindoles
Dong, Kuiyong; Pei, Chao; Zeng, Qian; Wei, Hanlin; Doyle, Michael P.; Xu, Xinfang; ACS Catalysis 8 (2018) 9543–; doi:10.1021/acscatal.8b02822

data_4515537
_publ_section_title
;
 Selective C(sp3)--H Bond Insertion in Carbene/Alkyne Metathesis
 Reactions. Enantioselective Construction of Dihydroindoles
;
_journal_issue                   10
_journal_name_full               'ACS Catalysis'
_journal_page_first              9543
_journal_paper_doi               10.1021/acscatal.8b02822
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H20 Cl N O2'
_chemical_formula_sum            'C25 H20 Cl N O2'
_chemical_formula_weight         401.87
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-03-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.12.12 svn.r3370 for OlexSys, GUI svn.r5282)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.12850(10)
_cell_length_b                   10.8042(2)
_cell_length_c                   30.5592(6)
_cell_measurement_reflns_used    9865
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      5.97
_cell_volume                     2023.43(6)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      119.96
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            13648
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.293
_diffrn_reflns_theta_min         5.970
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.835
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5308
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1519 before and 0.0724 after correction. The Ratio of minimum to maximum transmission is 0.7048. The \l/2 correction factor is Not present.'
_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    1.319
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1426 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.053(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3603
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0262
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0232P)^2^+0.4305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0661
_refine_ls_wR_factor_ref         0.0666
_reflns_Friedel_coverage         0.682
_reflns_Friedel_fraction_full    0.952
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                3536
_reflns_number_total             3603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b02822_si_003.cif
_cod_data_source_block           cu_dky0312c_0m
_cod_database_code               4515537
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.710
_shelx_estimated_absorpt_t_min   0.710
_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:
 C5(H5), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15), C17(H17), C18(H18),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_olex2_submission_special_instructions 'No special instructions were received'