Palladium-Catalyzed Synthesis of 3-Haloindol-2-amines from 3-Diazoindolin-2-imines and Alkyl Halides.
Zhou, Yuxuan; Li, Zhenmin; Ma, Fanghui; Zhao, Chang; Lu, Ping; Wang, Yanguang; The Journal of organic chemistry 84 (2019) 6655–6668; doi:10.1021/acs.joc.9b00191

data_4033601
_publ_section_title
;
 Palladium-Catalyzed Synthesis of 3-Haloindol-2-amines from
 3-Diazoindolin-2-imines and Alkyl Halides.
;
_journal_issue                   11
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6655
_journal_page_last               6668
_journal_paper_doi               10.1021/acs.joc.9b00191
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H19 Br N2 O3 S'
_chemical_formula_sum            'C23 H19 Br N2 O3 S'
_chemical_formula_weight         483.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-27
_audit_creation_method
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Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5381)
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_cell_angle_alpha                90
_cell_angle_beta                 108.99(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.302(2)
_cell_length_b                   7.7678(10)
_cell_length_c                   13.039(3)
_cell_measurement_reflns_used    1228
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.1515
_cell_measurement_theta_min      3.2267
_cell_volume                     1082.4(4)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -38.00   53.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683   38.0000    0.0000 91

  2 omega  -85.00    8.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  -38.0000 -180.0000 93
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0113564000
_diffrn_orient_matrix_UB_12      -0.0600993000
_diffrn_orient_matrix_UB_13      -0.0366527000
_diffrn_orient_matrix_UB_21      0.0413105000
_diffrn_orient_matrix_UB_22      -0.0460841000
_diffrn_orient_matrix_UB_23      0.0441615000
_diffrn_orient_matrix_UB_31      -0.0507099000
_diffrn_orient_matrix_UB_32      -0.0510791000
_diffrn_orient_matrix_UB_33      0.0033068000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            4591
_diffrn_reflns_point_group_measured_fraction_full 0.781
_diffrn_reflns_point_group_measured_fraction_max 0.778
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.347
_diffrn_reflns_theta_min         3.233
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.022
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86487
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
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    1.483
_exptl_crystal_description       block
_exptl_crystal_F_000             492
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.368
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 670 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3103
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0464P)^2^+0.1764P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1034
_refine_ls_wR_factor_ref         0.1199
_reflns_Friedel_coverage         0.447
_reflns_Friedel_fraction_full    0.528
_reflns_Friedel_fraction_max     0.522
_reflns_number_gt                2533
_reflns_number_total             3103
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00191_si_003.cif
_cod_data_source_block           180327_zyx427012_1
_cod_depositor_comments
'Adding full bibliography for 4033600--4033601.cif.'
_cod_database_code               4033601
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h o n s br'
_shelx_estimated_absorpt_t_max   0.582
_shelx_estimated_absorpt_t_min   0.444
_reflns_odcompleteness_completeness 99.54
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              85716
_shelx_hkl_checksum              34290
_olex2_submission_special_instructions 'No special instructions were received'