Enantioselective Aerobic Oxidative C(sp3)–H Olefination of Amines via Cooperative Photoredox and Asymmetric Catalysis
Wei, Guo; Zhang, Chenhao; Bureš, Filip; Ye, Xinyi; Tan, Choon-Hong; Jiang, Zhiyong; ACS Catalysis 6 (2016) 3708–; doi:10.1021/acscatal.6b00846

data_4513882
_publ_section_title
;
 Enantioselective Aerobic Oxidative C(sp3)--H Olefination of Amines via
 Cooperative Photoredox and Asymmetric Catalysis
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3708
_journal_paper_doi               10.1021/acscatal.6b00846
_journal_volume                  6
_journal_year                    2016
_chemical_formula_moiety         'C35 H30 Br N3 O2'
_chemical_formula_sum            'C35 H30 Br N3 O2'
_chemical_formula_weight         604.53
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                102.003(3)
_cell_angle_beta                 107.216(3)
_cell_angle_gamma                99.873(3)
_cell_formula_units_Z            2
_cell_length_a                   10.6203(4)
_cell_length_b                   11.0296(4)
_cell_length_c                   13.8669(5)
_cell_measurement_reflns_used    12239
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.3776
_cell_measurement_theta_min      3.4676
_cell_volume                     1469.68(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega  -32.00   -7.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.4438  -77.0000  120.0000 25

  2 omega   -2.00   95.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.4438 -125.0000  -60.0000 97

  3 omega  -22.00   67.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.4438  -77.0000   90.0000 89

  4 omega   10.00  114.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.4438   62.0000 -140.0000 104

  5 omega    7.00   39.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.4438   77.0000  -30.0000 32

  6 omega   14.00  114.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.4438   38.0000  120.0000 100

  7 omega   43.00  119.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.4438   77.0000  -30.0000 76

  8 omega  -38.00  -12.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -50.0000  -89.0000  103.0000 26

  9 omega  -45.00  -19.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -54.0000  -83.0000    7.0000 26

 10 omega  -45.00  -19.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -54.0000  -82.0000  -90.0000 26

 11 omega  -45.00  -19.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -54.0000  -83.0000 -163.0000 26

 12 omega  -50.00  -25.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000  -80.0000  113.0000 25

 13 omega  -50.00  -25.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -58.0000  -80.0000  -90.0000 25

 14 omega   28.00   55.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   77.0000   90.0000 27

 15 omega  114.00  139.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   77.0000   90.0000 25

 16 omega  -55.00  -28.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -62.0000  -78.0000  170.0000 27

 17 omega  -59.00  -32.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -66.0000  -78.0000 -112.0000 27

 18 omega -140.00 -115.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -66.0000  -78.0000 -112.0000 25

 19 omega -141.00 -115.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -70.0000  -77.0000   22.0000 26

 20 omega  -62.00  -36.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -70.0000  -77.0000  140.0000 26

 21 omega  -64.00  -37.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -70.0000  -77.0000   22.0000 27

 22 omega  -65.00  -38.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -70.0000  -76.0000   56.0000 27

 23 omega  -67.00  -41.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -74.0000  -74.0000  -25.0000 26

 24 omega  -66.00  -40.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -74.0000  -77.0000   98.0000 26

 25 omega  -67.00  -41.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -74.0000  -74.0000 -159.0000 26

 26 omega -134.00 -108.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -74.0000  -74.0000 -159.0000 26

 27 omega  -70.00  -44.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -78.0000  -79.0000  -29.0000 26

 28 omega  -70.00  -44.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -78.0000  -79.0000  153.0000 26

 29 omega  -72.00  -45.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -78.0000  -74.0000  -54.0000 27

 30 omega  -70.00  -44.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -78.0000  -79.0000   89.0000 26

 31 omega  -74.00  -48.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -82.0000  -79.0000 -169.0000 26

 32 omega  -75.00  -49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -82.0000  -75.0000  133.0000 26

 33 omega  -74.00  -48.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -82.0000  -78.0000  -66.0000 26

 34 omega  -75.00  -49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -78.0000 -113.0000 26

 35 omega  -75.00  -49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -78.0000 -155.0000 26

 36 omega  -76.00  -50.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -75.0000   11.0000 26

 37 omega  -85.00  -49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -78.0000   44.0000 36

 38 omega -119.00  -94.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  124.0000 -151.0000 25

 39 omega  -74.00  -49.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 25

 40 omega   97.00  161.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -150.0000 64

 41 omega   60.00   94.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -150.0000 34

 42 omega   98.00  151.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  150.0000 53

 43 omega   92.00  162.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   90.0000 70

 44 omega   60.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   90.0000 29

 45 omega   63.00  137.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   30.0000 74

 46 omega   96.00  152.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -90.0000 56

 47 omega   61.00   87.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -90.0000 26

 48 omega   64.00  171.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   60.0000 107

 49 omega   96.00  155.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  120.0000 59

 50 omega   60.00   86.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  120.0000 26

 51 omega   92.00  147.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -120.0000 55

 52 omega   63.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -120.0000 26

 53 omega  144.00  172.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -30.0000 28

 54 omega   61.00  141.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -30.0000 80

 55 omega   62.00  132.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -180.0000 70

 56 omega   94.00  171.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000    0.0000 77

 57 omega   60.00   86.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000    0.0000 26

 58 omega   66.00   92.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  150.0000 26

 59 omega   61.00  171.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -60.0000 110

 60 omega   86.00  131.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000  -83.0000 45

 61 omega   17.00   56.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000  -83.0000 39

 62 omega   32.00   76.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  -60.0000 44

 63 omega   83.00  110.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000   31.0000 27

 64 omega   30.00   77.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000   60.0000 47

 65 omega   38.00   66.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000   31.0000 28

 66 omega   43.00  127.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000 -150.0000 84

 67 omega    9.00  111.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -87.0000   59.0000 102

 68 omega   43.00  104.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -82.0000  132.0000 61
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1463163000
_diffrn_orient_matrix_UB_12      -0.0642818000
_diffrn_orient_matrix_UB_13      -0.0762653000
_diffrn_orient_matrix_UB_21      -0.0017947000
_diffrn_orient_matrix_UB_22      0.1179767000
_diffrn_orient_matrix_UB_23      -0.0429877000
_diffrn_orient_matrix_UB_31      0.0563924000
_diffrn_orient_matrix_UB_32      -0.0607685000
_diffrn_orient_matrix_UB_33      -0.0834813000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            27839
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.492
_diffrn_reflns_theta_max         67.492
_diffrn_reflns_theta_min         3.471
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.190
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67799
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.920
_refine_diff_density_min         -1.044
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         5245
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0593
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0963P)^2^+1.1854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1714
_refine_ls_wR_factor_ref         0.1817
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4437
_reflns_number_total             5245
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b00846_si_002.cif
_cod_data_source_block           151014_wg640_3
_cod_depositor_comments          'Adding full bibliography for 4513882.cif.'
_cod_original_cell_volume        1469.67(9)
_cod_database_code               4513882
_chemical_oxdiff_formula         'c10 h10 n2 o8 Br1'
_shelx_estimated_absorpt_t_max   0.560
_shelx_estimated_absorpt_t_min   0.432
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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 Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C16(H16), C17(H17), C19(H19), C20(H20),
 C21(H21), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C30(H30), C31(H31),
  C33(H33), C34(H34)
2.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C)
;
_shelx_res_checksum              79976
_shelx_hkl_checksum              7250
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'