Palladium-catalyzed intramolecular Heck dearomative <i>gem</i>-difluorovinylation of indoles.
Wang, Gang; Li, Wenqi; Liu, Tianxiang; Zhang, Yonghong; Wang, Bin; Xue, Fei; Jin, Weiwei; Ma, Caiyan; Xia, Yu; Liu, Chenjiang; Chemical science 13 (2022) 11594–11599; doi:10.1039/d2sc03169h

data_1567632
_publ_section_title
;
 Palladium-catalyzed intramolecular Heck dearomative
 <i>gem</i>-difluorovinylation of indoles.
;
_journal_issue                   39
_journal_name_full               'Chemical science'
_journal_page_first              11594
_journal_page_last               11599
_journal_paper_doi               10.1039/d2sc03169h
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C25 H30 N2 O2'
_chemical_formula_sum            'C25 H30 N2 O2'
_chemical_formula_weight         390.51
_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_Hall           'P -4 2n'
_space_group_name_H-M_alt        'P -4 21 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-14
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6383)
;
_audit_update_record
;
2021-08-14 deposited with the CCDC.	2022-09-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.1920(8)
_cell_length_b                   20.1920(8)
_cell_length_c                   11.0430(5)
_cell_measurement_reflns_used    2911
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      27.156
_cell_measurement_theta_min      2.253
_cell_volume                     4502.4(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1637
_diffrn_reflns_av_unetI/netI     0.1123
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            21458
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.734
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.073
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1144 before and 0.0535 after correction.
The Ratio of minimum to maximum transmission is 0.8023.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.152
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_refine_diff_density_max         0.140
_refine_diff_density_min         -0.143
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 587 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.4(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.952
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         3966
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.952
_refine_ls_R_factor_all          0.1518
_refine_ls_R_factor_gt           0.0709
_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^)+(0.0707P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1481
_refine_ls_wR_factor_ref         0.1737
_reflns_Friedel_coverage         0.791
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1958
_reflns_number_total             3966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03169h2.cif
_cod_data_source_block           1_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1567630--1567632.cif.'
_cod_original_cell_volume        4502.4(4)
_cod_database_code               1567632
_shelx_shelxl_version_number     2018/3
_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:
 C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C11(H11A,H11B), C16(H16A,H16B), C19(H19A,H19B),
 C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C7(H7), C9(H9), C12(H12), C14(H14), C17(H17), C21(H21)
2.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              67185
_shelx_hkl_checksum              3416
_olex2_submission_special_instructions 'No special instructions were received'