Iron-Catalyzed Aerobic Dehydrogenative Kinetic Resolution of Cyclic Secondary Amines.
Lu, Ran; Cao, Liya; Guan, Honghao; Liu, Lei; Journal of the American Chemical Society 141 (2019) 6318–6324; doi:10.1021/jacs.9b00615

data_4128664
_publ_section_title
;
 Iron-Catalyzed Aerobic Dehydrogenative Kinetic Resolution of Cyclic
 Secondary Amines.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6318
_journal_page_last               6324
_journal_paper_doi               10.1021/jacs.9b00615
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C66 H56 Br4 Fe2 N4 O6'
_chemical_formula_sum            'C66 H56 Br4 Fe2 N4 O6'
_chemical_formula_weight         1432.49
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-30
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                79.166(2)
_cell_angle_beta                 83.628(2)
_cell_angle_gamma                83.716(2)
_cell_formula_units_Z            1
_cell_length_a                   11.5182(3)
_cell_length_b                   12.6576(4)
_cell_length_c                   12.8574(4)
_cell_measurement_reflns_used    12785
_cell_measurement_temperature    128(20)
_cell_measurement_theta_max      70.9160
_cell_measurement_theta_min      6.6830
_cell_volume                     1822.18(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'J. Appl. Cryst. (2007). 40, 609-613'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      128(20)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0793
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9992
_diffrn_measured_fraction_theta_max 0.8761
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     23.00  66.00   1.00    1.00    --    0.00  19.00   0.00   43
  2  \w     38.00  63.00   1.00    1.00    --    0.00  57.00  60.00   25
  3  \w     24.00 122.00   1.00    1.00    --   54.00  77.00 150.00   98
  4  \w     80.00 119.00   1.00    1.00    --   54.00  77.00  60.00   39
  5  \w     78.00 105.00   1.00    1.00    --   54.00  77.00 120.00   27
  6  \w     77.00 115.00   1.00    1.00    --   54.00  77.00  30.00   38
  7  \w     75.00 117.00   1.00    1.00    --   54.00  77.00   0.00   42
  8  \w     76.00 119.00   1.00    1.00    --   54.00  77.00 -30.00   43
  9  \w     79.00 174.00   1.00    1.00    --  108.00  77.00 -60.00   95
 10  \w    136.00 177.00   1.00    1.00    --  108.00  77.00   0.00   41
 11  \w    137.00 164.00   1.00    1.00    --  108.00  74.00  84.92   27
 12  \w    124.00 178.00   1.00    1.00    --  108.00  77.00  30.00   54
 13  \w    111.00 170.00   1.00    1.00    --  108.00  77.00 -30.00   59
 14  \w    140.00 168.00   1.00    1.00    --  108.00  77.00-150.00   28
 15  \w    113.00 177.00   1.00    1.00    --  108.00  77.00-180.00   64
 16  \w     86.00 151.00   1.00    1.00    --  108.00  63.00   0.00   65
 17  \w     86.00 113.00   1.00    1.00    --  108.00  63.00 120.00   27
 18  \w    110.00 176.00   1.00    1.00    --  108.00  77.00 150.00   66
 19  \w     88.00 117.00   1.00    1.00    --  108.00  53.00 123.33   29
 20  \w     86.00 155.00   1.00    1.00    --  108.00  63.00  60.00   69
 21  \w     89.00 121.00   1.00    1.00    --  108.00  50.00  60.00   32
 22  \w     83.00 113.00   1.00    1.00    --  108.00  37.00   0.00   30
 23  \w     80.00 106.00   1.00    1.00    --  108.00  74.00  84.92   26
 24  \w     78.00 104.00   1.00    1.00    --  108.00  77.00  60.00   26
 25  \w     78.00 112.00   1.00    1.00    --  108.00  77.00  90.00   34
 26  \w     78.00 105.00   1.00    1.00    --  108.00  77.00 150.00   27
 27  \w     78.00 178.00   1.00    1.00    --  108.00  77.00 120.00  100
 28  \w     79.00 107.00   1.00    1.00    --  108.00  75.00  14.61   28
 29  \w     78.00 104.00   1.00    1.00    --  108.00  77.00 -30.00   26
 30  \w     78.00 104.00   1.00    1.00    --  108.00  77.00   0.00   26
 31  \w     78.00 104.00   1.00    1.00    --  108.00  77.00  30.00   26
 32  \w     80.00 106.00   1.00    1.00    --  108.00  73.00 -65.22   26
 33  \w     86.00 113.00   1.00    1.00    --  108.00  63.00 -90.00   27
 34  \w     82.00 147.00   1.00    1.00    --  108.00  37.00-120.00   65
 35  \w     87.00 112.00   1.00    1.00    --  108.00  63.00-150.00   25
 36  \w     86.00 112.00   1.00    1.00    --  108.00  63.00-180.00   26
 37  \w     78.00 104.00   1.00    1.00    --  108.00  77.00-180.00   26
 38  \w     82.00 176.00   1.00    1.00    --  108.00  70.00-125.80   94
 39  \w     81.00 121.00   1.00    1.00    --   54.00  77.00-180.00   40
 40  \w     78.00 105.00   1.00    1.00    --  108.00  77.00-150.00   27
 41  \w     82.00 108.00   1.00    1.00    --  108.00  37.00-180.00   26
 42  \w     78.00 105.00   1.00    1.00    --  108.00  77.00-120.00   27
 43  \w     78.00 177.00   1.00    1.00    --  108.00  77.00 -90.00   99
 44  \w     64.00 105.00   1.00    1.00    --   54.00  77.00 -60.00   41
 45  \w     41.00  72.00   1.00    1.00    --    0.00  37.00-180.00   31
 46  \w     24.00 118.00   1.00    1.00    --   54.00  77.00-120.00   94
 47  \w     58.00 136.00   1.00    1.00    --  108.00 178.00  30.00   78
 48  \w     25.00  61.00   1.00    1.00    --   54.00  77.00 -60.00   36
 49  \w     24.00  61.00   1.00    1.00    --   54.00  77.00   0.00   37
 50  \w     25.00  50.00   1.00    1.00    --   54.00  77.00  60.00   25
 51  \w     25.00  51.00   1.00    1.00    --   54.00  77.00  90.00   26
 52  \w     24.00  76.00   1.00    1.00    --   54.00  77.00 120.00   52
 53  \w     25.00  60.00   1.00    1.00    --   54.00  77.00  30.00   35
 54  \w     24.00  50.00   1.00    1.00    --   54.00  77.00 -30.00   26
 55  \w     23.00  48.00   1.00    1.00    --   54.00  78.00 -94.87   25
 56  \w     24.00  63.00   1.00    1.00    --   54.00  77.00-150.00   39
 57  \w     25.00  52.00   1.00    1.00    --   54.00  77.00-180.00   27
 58  \w    -19.00  40.00   1.00    1.00    --    0.00  37.00-180.00   59
 59  \w     -5.00  32.00   1.00    1.00    --    0.00  57.00  60.00   37
 60  \w    -44.00  14.00   1.00    1.00    --    0.00  19.00   0.00   58
 61  \w    -12.00  72.00   1.00    1.00    --   54.00 -57.00  90.00   84
 62  \w     53.00 137.00   1.00    1.00    --  108.00 -77.00  90.00   84
 63  \w    111.00 145.00   1.00    1.00    --  108.00 -91.00 -30.00   34
 64  \w     75.00 102.00   1.00    1.00    --  108.00-111.00-150.00   27
 65  \w     59.00 116.00   1.00    1.00    --  108.00-111.00 -90.00   57
 66  \w     57.00 116.00   1.00    1.00    --  108.00-111.00  60.00   59
 67  \w     38.00  90.00   1.00    1.00    --  108.00 -91.00 -30.00   52
 68  \w      2.00  91.00   1.00    1.00    --   54.00 -99.00  60.00   89
 69  \w      1.00  89.00   1.00    1.00    --   54.00 -99.00-120.00   88
 70  \w    -10.00  73.00   1.00    1.00    --   54.00 -57.00 -90.00   83
 71  \w    -39.00  13.00   1.00    1.00    --    0.00 -57.00-150.00   52
 72  \w    -51.00  16.00   1.00    1.00    --    0.00 -77.00  30.00   67
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0487550000
_diffrn_orient_matrix_UB_12      0.1093442000
_diffrn_orient_matrix_UB_13      -0.0036024000
_diffrn_orient_matrix_UB_21      0.0598336000
_diffrn_orient_matrix_UB_22      -0.0048668000
_diffrn_orient_matrix_UB_23      -0.1124834000
_diffrn_orient_matrix_UB_31      -0.1109306000
_diffrn_orient_matrix_UB_32      0.0591916000
_diffrn_orient_matrix_UB_33      -0.0484321000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            25642
_diffrn_reflns_theta_full        67.08
_diffrn_reflns_theta_max         70.94
_diffrn_reflns_theta_min         3.52
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.129
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25354
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.836
_refine_diff_density_min         -0.931
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.000(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     728
_refine_ls_number_reflns         11704
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0662
_refine_ls_R_factor_gt           0.0607
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1342P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1715
_refine_ls_wR_factor_ref         0.1808
_reflns_number_gt                10583
_reflns_number_total             11704
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b00615_si_002.cif
_cod_data_source_block           exp_2530_sqd
_cod_original_cell_volume        1822.17(9)
_cod_database_code               4128664
_chemical_oxdiff_formula         'C1 H1 O1 N1 Fe1 Br1'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C15(H15), C36(H36), C43(H43), N1(H1), N2(H2), N3(H3A), N4(H4A)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C22(H22A,H22B), C35(H35A,H35B), C50(H50A,H50B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C24(H24), C25(H25), C26(H26),
  C31(H31), C32(H32), C33(H33), C38(H38), C39(H39), C40(H40), C41(H41),
 C42(H42), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C52(H52), C53(H53),
  C54(H54), C58(H58), C59(H59), C60(H60), C63(H63), C64(H64), C65(H65),
 C66(H66), O1(H1A)
2.d Fitted hexagon refined as free rotating group:
 C61(C62,C63,C64,C65,C66)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.439
_oxdiff_exptl_absorpt_empirical_full_min 0.488