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_4128665
_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         'C56 H50 Br4 Fe2 N4 O6, 7(C2 H3 N)'
_chemical_formula_sum            'C70 H71 Br4 Fe2 N11 O6'
_chemical_formula_weight         1593.72
_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     iterative
_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                80.061(6)
_cell_angle_beta                 84.900(6)
_cell_angle_gamma                84.005(6)
_cell_formula_units_Z            1
_cell_length_a                   11.3961(8)
_cell_length_b                   12.6727(9)
_cell_length_c                   12.8895(10)
_cell_measurement_reflns_used    7334
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      70.8970
_cell_measurement_theta_min      5.4360
_cell_volume                     1818.8(2)
_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
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0793
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9989
_diffrn_measured_fraction_theta_max 0.6072
_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    -20.00  10.00   1.00    1.00    --    0.00 -57.00   0.00   30
  2  \w     31.00  78.00   1.00    1.00    --   54.00-125.00  90.00   47
  3  \w     39.00 127.00   1.00    1.00    --  108.00 -77.00  90.00   88
  4  \w     81.00 109.00   1.00    1.00    --  108.00 -63.00   0.00   28
  5  \w     64.00 109.00   1.00    1.00    --  108.00-111.00   0.00   45
  6  \w     56.00 128.00   1.00    1.00    --  108.00 -37.00  60.00   72
  7  \w    141.00 171.00   1.00    1.00    --  108.00  25.00 150.00   30
  8  \w    118.00 169.00   1.00    1.00    --  108.00 -12.00 150.00   51
  9  \w     98.00 175.00   1.00    1.00    --  108.00  63.00  30.00   77
 10  \w    121.00 172.00   1.00    1.00    --  108.00  50.00   0.00   51
 11  \w     74.00 105.00   1.00    1.00    --  108.00  25.00 150.00   31
 12  \w     78.00 172.00   1.00    1.00    --  108.00  77.00  60.00   94
 13  \w     45.00  70.00   1.00    1.00    --  108.00 -63.00   0.00   25
 14  \w     38.00 143.00   1.00    1.00    --  108.00 -91.00 -60.00  105
 15  \w     78.00 110.00   1.00    1.00    --  108.00-111.00-120.00   32
 16  \w     37.00  66.00   1.00    1.00    --  108.00-111.00-120.00   29
 17  \w     37.00  96.00   1.00    1.00    --  108.00-111.00 -90.00   59
 18  \w     36.00 110.00   1.00    1.00    --  108.00 -37.00 -90.00   74
 19  \w     34.00 103.00   1.00    1.00    --   54.00  57.00-150.00   69
 20  \w     25.00 102.00   1.00    1.00    --   54.00  77.00 -30.00   77
 21  \w     37.00 114.00   1.00    1.00    --   54.00  57.00  60.00   77
 22  \w     33.00  69.00   1.00    1.00    --    0.00  57.00 150.00   36
 23  \w    -20.00  27.00   1.00    1.00    --    0.00  57.00 150.00   47
 24  \w    -68.00 -35.00   1.00    1.00    --    0.00 -57.00   0.00   33
 25  \w      2.00  96.00   1.00    1.00    --   54.00 -99.00 150.00   94
 26  \w     75.00 114.00   1.00    1.00    --  108.00-111.00 119.00   39
 27  \w      8.00  33.00   1.00    1.00    --    0.00  57.00-120.00   25
 28  \w     25.00 120.00   1.00    1.00    --   54.00  77.00 -90.00   95
;
_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      0.0088673000
_diffrn_orient_matrix_UB_12      -0.0189420000
_diffrn_orient_matrix_UB_13      -0.1154350000
_diffrn_orient_matrix_UB_21      -0.0928448000
_diffrn_orient_matrix_UB_22      -0.0823265000
_diffrn_orient_matrix_UB_23      0.0289318000
_diffrn_orient_matrix_UB_31      -0.0993729000
_diffrn_orient_matrix_UB_32      0.0906761000
_diffrn_orient_matrix_UB_33      -0.0252599000
_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  0.0285
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12745
_diffrn_reflns_theta_full        67.08
_diffrn_reflns_theta_max         71.02
_diffrn_reflns_theta_min         3.49
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.228
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47530
_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 red'
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.962
_refine_diff_density_min         -0.812
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.008(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     839
_refine_ls_number_reflns         8165
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0469
_refine_ls_shift/su_max          0.023
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0990P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1266
_refine_ls_wR_factor_ref         0.1283
_reflns_number_gt                7858
_reflns_number_total             8165
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b00615_si_003.cif
_cod_data_source_block           exp_2573_sqd
_cod_database_code               4128665
_chemical_oxdiff_formula         'C1 H1 O1 N1 Br1 Fe1'
_reflns_odcompleteness_completeness 99.89
_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
 At 1.5 times of:
  All C(H,H,H) groups, All N(H,H) groups
2. Restrained distances
 C57-C58 = C67-C68 = C63-C64 = C66-C65
 1.53 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(N5) \\sim Ueq, Uanis(N6) \\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C26) = Uanis(C20)
4.a Riding coordinates:
 N1(H1), N2(H2A), N3(H3A), N4(H4A), N6(H6,H5)
4.b Ternary CH refined with riding coordinates:
 C8(H8), C15(H15), C36(H36), C43(H43)
4.c Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C22(H22A,H22B), C35(H35A,H35B), C50(H50A,H50B)
4.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), 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),
  C30(H30), C31(H31), C32(H32), 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)
4.e Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C61(H61A,H61B,H61C), C63(H63A,H63B,
 H63C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C)
;
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.792
_oxdiff_exptl_absorpt_empirical_full_min 0.680