Iron-Catalyzed Asymmetric Haloazidation of α,β-Unsaturated Ketones: Construction of Organic Azides with Two Vicinal Stereocenters.
Zhou, Pengfei; Lin, Lili; Chen, Long; Zhong, Xia; Liu, Xiaohua; Feng, Xiaoming; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b06029

data_4126415
_publ_section_title
;
 Iron-Catalyzed Asymmetric Haloazidation of \a,\b-Unsaturated Ketones:
 Construction of Organic Azides with Two Vicinal Stereocenters.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b06029
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H12 Br N3 O'
_chemical_formula_sum            'C15 H12 Br N3 O'
_chemical_formula_weight         330.19
_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     direct
_audit_creation_date             2016-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.354(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.4448(2)
_cell_length_b                   5.7199(2)
_cell_length_c                   16.4982(7)
_cell_measurement_reflns_used    2322
_cell_measurement_temperature    293.5(2)
_cell_measurement_theta_max      71.5520
_cell_measurement_theta_min      5.3670
_cell_volume                     702.54(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      air
_diffrn_ambient_temperature      293.5(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -99.0000   90.0000 74

  2 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -57.0000   60.0000 84

  3 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -57.0000    0.0000 84

  4 omega    9.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000  -90.0000 95

  5 omega  -35.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -19.0000  150.0000 101

  6 omega  -31.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -77.0000  150.0000 94

  7 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -99.0000  -30.0000 74

  8 omega   38.00   91.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 53

  9 omega   87.00  178.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -120.0000 91

 10 omega   39.00  109.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -120.0000 70

 11 omega   38.00   91.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 53

 12 omega   39.00  109.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 70

 13 omega   38.00   91.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   30.0000 53

 14 omega   39.00  109.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 70

 15 omega   38.00   91.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 53

 16 omega   40.00   98.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 58

 17 omega   40.00   98.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

 18 omega   38.00   91.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 53

 19 omega   40.00   98.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 58

 20 omega   38.00   91.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   90.0000 53

 21 omega   40.00  135.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   30.0000 95

 22 omega   37.00  146.00   1.0000    1.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000 -150.0000 109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.2013093000
_diffrn_orient_matrix_UB_12      0.0249198000
_diffrn_orient_matrix_UB_13      -0.0192968000
_diffrn_orient_matrix_UB_21      0.0463578000
_diffrn_orient_matrix_UB_22      -0.0409283000
_diffrn_orient_matrix_UB_23      0.0899875000
_diffrn_orient_matrix_UB_31      0.0117137000
_diffrn_orient_matrix_UB_32      -0.2650982000
_diffrn_orient_matrix_UB_33      -0.0157368000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0338
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            5421
_diffrn_reflns_point_group_measured_fraction_full 0.733
_diffrn_reflns_point_group_measured_fraction_max 0.712
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.294
_diffrn_reflns_theta_min         5.363
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.980
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39338
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.561
_exptl_crystal_description       plate
_exptl_crystal_F_000             332
_exptl_crystal_size_max          0.65
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.805
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 433 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     181
_refine_ls_number_reflns         1981
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0920P)^2^+0.0040P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1292
_reflns_Friedel_coverage         0.306
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_reflns_Friedel_fraction_max     0.373
_reflns_number_gt                1915
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_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06029_si_002.cif
_cod_data_source_block           exp_2791
_cod_original_cell_volume        702.54(5)
_cod_database_code               4126415
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C19(H19), C26(H26), C0AA(H0AA), C1(H1), C3(H3), C4(H4),
 C5(H5), C6(H6)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-16
_olex2_submission_special_instructions 'No special instructions were received'