Enantioselective Iron-Catalyzed Azidation of β-Keto Esters and Oxindoles
Qing-Hai Deng; Tim Bleith; Hubert Wadepohl; Lutz H. Gade; Journal of the American Chemical Society 135 (2013) 5356–5359; doi:10.1021/ja402082p

data_4119570
_publ_section_title
;
 Enantioselective Iron-Catalyzed Azidation of \b-Keto Esters and Oxindoles
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5356
_journal_page_last               5359
_journal_paper_doi               10.1021/ja402082p
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_sum            'C35 H30 Fe N4 O4'
_chemical_formula_weight         626.48
_chemical_properties_physical    air-sensitive
_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'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_tb3
_audit_creation_date
;
'Fri Feb 15 17:16:21 2013'
;
_audit_creation_method           SHELXL-2012
_audit_update_record             'Fri Feb 15 19:21:21 CET 2013'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.06579(11)
_cell_length_b                   10.63399(13)
_cell_length_c                   30.8521(5)
_cell_measurement_reflns_used    25193
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      71.7120
_cell_measurement_theta_min      4.3800
_cell_volume                     2974.31(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_publication_material
'encif (Wadepohl, 2012); encifer 1.4 (CCDC, 2011)'
_computing_structure_refinement  'SHELXL-2012 (Sheldrick, 2012)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9241
_diffrn_detector_type            'Agilent EOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega  -68.00   14.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -30.0000 164

  2 omega    7.00   68.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   60.0000 122

  3 omega   -7.00   47.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       22.0000   77.0000  135.9742 108

  4 omega   11.00   41.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   79.0000  -29.0287 60

  5 omega   10.00   35.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   80.0000  151.8076 50

  6 omega  -40.00  -12.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000 -180.0000 56

  7 omega -112.00  -45.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   90.0000 134

  8 omega  -90.00  -63.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  -60.0000 54

  9 omega -112.00  -45.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000 -180.0000 134

 10 omega  -54.00  -12.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000  -60.0000 84

 11 omega  -50.00   30.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   38.0000 -150.0000 160

 12 omega  -39.00  -12.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   90.0000 54

 13 omega  -72.00   27.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   77.0000   90.0000 198

 14 omega   15.00   40.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   78.0000   -2.4914 50

 15 omega   19.00   47.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   79.0000 -125.0353 56

 16 omega   18.00   43.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000 -172.8693 50

 17 omega   19.00   45.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   78.0000   36.6570 52

 18 omega   18.00   44.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000   96.4048 52

 19 omega   18.00   43.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000  -70.7946 50

 20 omega   23.00   48.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   78.0000 -115.0022 50

 21 omega   23.00   48.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   78.0000  135.0789 50

 22 omega  103.00  128.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  158.7167 50

 23 omega   30.00   63.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000  -59.9192 66

 24 omega   28.00   55.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  158.7167 54

 25 omega   28.00   54.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  -23.4216 52

 26 omega   -9.00   93.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000  -80.0000 -128.7326 204

 27 omega   34.00   66.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   75.0000   35.8447 64

 28 omega   39.00   65.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   72.0000  -94.1583 52

 29 omega   -5.00   78.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000  -80.0000  -47.4238 166

 30 omega   36.00   70.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  104.9392 68

 31 omega   36.00   62.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  -16.4503 52

 32 omega  108.00  135.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  104.9392 54

 33 omega   37.00   63.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   76.0000 -160.9275 52

 34 omega   99.00  126.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  -16.4503 54

 35 omega   39.00   65.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   71.0000 -168.6546 52

 36 omega   98.00  125.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   66.0000  158.2852 54

 37 omega   47.00   73.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   66.0000  158.2852 52

 38 omega   46.00   71.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   69.0000   69.5966 50

 39 omega   46.00   73.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   42.0000   -0.0930 54

 40 omega   44.00   69.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   72.0000   89.4481 50

 41 omega   43.00   85.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   75.0000 -133.6407 84

 42 omega   45.00  111.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   77.0000  -83.0989 132

 43 omega   47.00   74.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   71.0000    7.5250 54

 44 omega   51.00   80.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   73.0000   63.7786 58

 45 omega   50.00   98.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   73.0000 -150.8678 96

 46 omega   54.00   91.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   69.0000 -121.1664 74

 47 omega   50.00   75.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   75.0000  174.4379 50

 48 omega  117.00  142.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   61.0000   44.1434 50

 49 omega   56.00  100.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   61.0000   44.1434 88

 50 omega   50.00  118.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       78.0000   74.0000   97.6384 136

 51 omega   53.00   87.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000   77.0000  -97.7318 68

 52 omega   54.00   79.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       82.0000   76.0000  -16.4289 50

 53 omega   56.00   82.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       86.0000   77.0000  137.5584 52

 54 omega   59.00   85.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       86.0000   72.0000  -34.8866 52

 55 omega   42.00   93.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       86.0000  -80.0000   89.9387 102

 56 omega   64.00   94.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000   70.0000 -104.4939 60

 57 omega   67.00  138.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000   65.0000 -161.4669 142

 58 omega   64.00   89.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       90.0000   71.0000  -33.1440 50

 59 omega   77.00  103.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   62.0000  -89.5180 52

 60 omega   70.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   73.0000  -17.1065 52

 61 omega  109.00  145.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   53.0000  169.0262 72

 62 omega   77.00  104.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   53.0000  169.0262 54

 63 omega   75.00  103.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       98.0000   47.0000 -116.6759 56

 64 omega   74.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      102.0000   73.0000   -3.1532 52

 65 omega  125.00  152.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      102.0000   73.0000   32.1526 54

 66 omega   74.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      102.0000   73.0000   32.1526 52

 67 omega   80.00  177.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000   60.0000 194

 68 omega   53.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  146.5416 94

 69 omega   66.00  117.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000  -96.3900 102

 70 omega   66.00  113.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000   67.0079 94

 71 omega  116.00  141.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -79.0000   28.0650 50

 72 omega   62.00   97.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -79.0000   28.0650 70

 73 omega   55.00  110.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -80.0000 -160.7714 110

 74 omega   88.00  114.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000   90.0000 52

 75 omega   88.00  145.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   64.0000   60.0000 114

 76 omega   81.00  177.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -120.0000 192

 77 omega   80.00  178.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -180.0000 196

 78 omega   70.00  109.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342  -79.0000  -40.3462 78

 79 omega   80.00  177.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000    0.0000 194

 80 omega   80.00  178.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000   90.0000 196

 81 omega   80.00  174.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  120.0000 188

 82 omega   80.00  178.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000   30.0000 196

 83 omega   80.00  178.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000 -150.0000 196

 84 omega   80.00  178.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  150.0000 196

 85 omega   80.00  172.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -60.0000 184

 86 omega   81.00  177.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -30.0000 192

 87 omega   80.00  171.50   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      110.2342   77.0000  -90.0000 183

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      -0.1376544000
_diffrn_orient_matrix_UB_12      0.0784063000
_diffrn_orient_matrix_UB_13      0.0112642000
_diffrn_orient_matrix_UB_21      0.0735316000
_diffrn_orient_matrix_UB_22      0.1174934000
_diffrn_orient_matrix_UB_23      -0.0196351000
_diffrn_orient_matrix_UB_31      -0.0672940000
_diffrn_orient_matrix_UB_32      -0.0319342000
_diffrn_orient_matrix_UB_33      -0.0444885000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.070
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            76025
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.115
_diffrn_reflns_theta_min         4.398
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    4.448
_exptl_absorpt_correction_T_max  0.705
_exptl_absorpt_correction_T_min  0.535
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_description       plate
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.2125
_exptl_crystal_size_mid          0.1694
_exptl_crystal_size_min          0.1092
_refine_diff_density_max         0.777
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 2267 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.001(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         16684
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0712P)^2^+2.1895P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1251
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                15556
_reflns_number_total             16684
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja402082p_si_001_1.cif
_cod_data_source_block           ga_tb3_5
_cod_database_code               4119570
_audit_block_refno               1705
_audit_block_usercomment         'tb127, plate, black'
_shelx_estimated_absorpt_t_min   0.665
_shelx_estimated_absorpt_t_max   0.665
_shelxl_version_number           2012-6
_shelx_res_checksum              87082
_cell_oxdiff_length_a            9.06547(13)
_cell_oxdiff_length_b            10.63192(14)
_cell_oxdiff_length_c            30.8591(4)
_cell_oxdiff_angle_alpha         89.9977(11)
_cell_oxdiff_angle_beta          90.0110(12)
_cell_oxdiff_angle_gamma         89.9741(11)
_cell_oxdiff_volume              2974.31(7)
_cell_oxdiff_measurement_reflns_used 25556
_cell_oxdiff_twin_number         2