Rhodium(II)-Catalyzed Regioselective Remote C–H Alkylation of Protic Indoles
Kong, Lingheng; Han, Xi; Chen, Haohua; Sun, Huaming; Lan, Yu; Li, Xingwei; ACS Catalysis  (2021) 4929–4935; doi:10.1021/acscatal.1c01052

data_4518668
_publ_section_title
;
 Rhodium(II)-Catalyzed Regioselective Remote C--H Alkylation of Protic
 Indoles
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4929
_journal_page_last               4935
_journal_paper_doi               10.1021/acscatal.1c01052
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H16 Br N O, 0.25(H2 O)'
_chemical_formula_sum            'C24 H16.5 Br N O1.25'
_chemical_formula_weight         418.79
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2021-03-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                94.461(3)
_cell_angle_beta                 102.259(4)
_cell_angle_gamma                105.750(3)
_cell_formula_units_Z            4
_cell_length_a                   9.7726(9)
_cell_length_b                   12.1642(11)
_cell_length_c                   16.4042(15)
_cell_measurement_reflns_used    9532
_cell_measurement_temperature    153.0
_cell_measurement_theta_max      68.322
_cell_measurement_theta_min      2.785
_cell_volume                     1814.9(3)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      153.0
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.980
_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_unetI/netI     0.0539
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            12366
_diffrn_reflns_point_group_measured_fraction_full 0.932
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.773
_diffrn_reflns_theta_min         2.785
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.200
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5462
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1229 before and 0.0905 after correction.
The Ratio of minimum to maximum transmission is 0.7253.
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    1.533
_exptl_crystal_description       block
_exptl_crystal_F_000             850
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.792
_refine_diff_density_min         -1.031
_refine_diff_density_rms         0.171
_refine_ls_abs_structure_details
;
 Flack x determined using 4630 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.085(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     990
_refine_ls_number_reflns         12366
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0766
_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^)+(0.1076P)^2^+11.9152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2335
_refine_ls_wR_factor_ref         0.2410
_reflns_Friedel_coverage         0.876
_reflns_Friedel_fraction_full    0.874
_reflns_Friedel_fraction_max     0.859
_reflns_number_gt                11309
_reflns_number_total             12366
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01052_si_001.cif
_cod_data_source_block           s_tw
_cod_original_formula_sum        'C24 H16.50 Br N O1.25'
_cod_database_code               4518668
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.447
_shelx_estimated_absorpt_t_min   0.298
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.635(5)
 0.365(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Free rotating group:
 O010(H01B,H01C)
4.b Aromatic/amide H refined with riding coordinates:
 N007(H007), N009(H009), N00B(H00B), C00C(H00C), N00D(H00D), C00F(H00F),
 C00G(H00G), C00L(H00L), C00N(H00N), C00O(H00O), C00Q(H00Q), C00U(H00U),
 C00W(H00W), C00Y(H00Y), C012(H012), C017(H017), C019(H019), C01A(H01A),
 C01E(H01E), C01F(H01F), C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J),
 C01N(H01N), C01O(H01O), C01P(H01P), C01R(H01R), C01S(H01S), C01U(H01U),
 C01X(H01X), C01Y(H01Y), C020(H020), C023(H023), C024(H024), C025(H025),
 C026(H026), C029(H029), C02B(H02B), C02D(H02D), C02E(H02E), C02F(H02F),
 C02H(H02H), C02I(H02I), C02J(H02J), C02K(H02K), C02L(H02L), C02O(H02O),
 C02P(H02P), C02Q(H02Q), C02R(H02R), C02S(H02S), C02T(H02T), C02U(H02U),
 C02V(H02V), C02Y(H02Y), C02Z(H02Z), C031(H031), C033(H033), C35(H35)
4.c Idealised tetrahedral OH refined as rotating group:
 O005(H005), O006(H006), O008(H008), O00E(H00E)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              79499
_shelx_hkl_checksum              30467
_olex2_submission_special_instructions 'No special instructions were received'