Catalytic Asymmetric Umpolung Allylation of Imines.
Liu, Jie; Cao, Chao-Guo; Sun, Hong-Bao; Zhang, Xia; Niu, Dawen; Journal of the American Chemical Society 138 (2016) 13103–13106; doi:10.1021/jacs.6b05288

data_4130623
_publ_section_title
;
 Catalytic Asymmetric Umpolung Allylation of Imines.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13103
_journal_page_last               13106
_journal_paper_doi               10.1021/jacs.6b05288
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Cl, C16 H16 Cl2 N'
_chemical_formula_sum            'C16 H16 Cl3 N'
_chemical_formula_weight         328.65
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.719(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.5249(3)
_cell_length_b                   5.8864(2)
_cell_length_c                   14.3094(4)
_cell_measurement_reflns_used    4077
_cell_measurement_temperature    293
_cell_measurement_theta_max      72.5090
_cell_measurement_theta_min      5.1530
_cell_volume                     788.29(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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
  1 omega   20.00  104.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000    0.0000 84

  2 omega   23.00   90.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000 -150.0000 67

  3 omega  -31.00   53.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000   30.0000 84

  4 omega   10.00  104.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000  120.0000 94

  5 omega  -11.00  106.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   11.0000    4.0000 117

  6 omega   20.00  104.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000 -120.0000 84

  7 omega   17.00  105.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   38.0000   30.0000 88

  8 omega   20.00  104.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000 -180.0000 84

  9 omega   10.00  104.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000   60.0000 94

 10 omega  -31.00   53.00   1.0000    2.2900
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000  120.0000 84

 11 omega   81.00  176.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 95

 12 omega   81.00  176.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 95

 13 omega   87.00  178.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  120.0000 91

 14 omega   81.00  176.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 95

 15 omega   70.00  178.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  120.0000 108

 16 omega   81.00  107.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 26

 17 omega   90.00  128.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 38

 18 omega  142.00  168.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 26

 19 omega  133.00  172.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 39

 20 omega   90.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   90.0000 26

 21 omega   41.00   96.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   30.0000 55

 22 omega   90.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 26

 23 omega   93.00  119.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 26

 24 omega   72.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   90.0000 26

 25 omega   90.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   60.0000 26

 26 omega   88.00  122.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 34

 27 omega  118.00  172.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 54

 28 omega  117.00  143.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 29 omega   40.00   92.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 52

 30 omega   82.00  108.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 31 omega   90.00  119.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  150.0000 29

 32 omega   41.00  104.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 63

 33 omega   91.00  117.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   30.0000 26

 34 omega   94.00  120.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  120.0000 26

 35 omega   82.00  108.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 36 omega   88.00  114.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 26

 37 omega   46.00   89.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 43
;
_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      -0.1390187000
_diffrn_orient_matrix_UB_12      -0.0106335000
_diffrn_orient_matrix_UB_13      -0.0746573000
_diffrn_orient_matrix_UB_21      -0.0876622000
_diffrn_orient_matrix_UB_22      0.0423560000
_diffrn_orient_matrix_UB_23      0.0786348000
_diffrn_orient_matrix_UB_31      0.0085927000
_diffrn_orient_matrix_UB_32      0.2580203000
_diffrn_orient_matrix_UB_33      -0.0159838000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            7744
_diffrn_reflns_point_group_measured_fraction_full 0.902
_diffrn_reflns_point_group_measured_fraction_max 0.880
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.455
_diffrn_reflns_theta_min         6.149
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.161
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34128
_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    1.385
_exptl_crystal_description       needle
_exptl_crystal_F_000             340
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.351
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 975 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.002(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         2748
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0481
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0991P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1281
_reflns_Friedel_coverage         0.620
_reflns_Friedel_fraction_full    0.782
_reflns_Friedel_fraction_max     0.751
_reflns_number_gt                2662
_reflns_number_total             2748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b05288_si_002.cif
_cod_data_source_block           yxq-lj-3
_cod_original_cell_volume        788.28(4)
_cod_database_code               4130623
_reflns_odcompleteness_completeness 99.81
_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
 At 1.5 times of:
  All N(H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C7(H7), C12(H12), C16(H16), C8(H8), C13(H13),
 C14(H14), C15(H15)
2.d Idealised tetrahedral OH refined as rotating group:
 N1(H1A)
;
_shelx_res_checksum              54964
_shelx_hkl_checksum              67963
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-05-05
_olex2_submission_special_instructions 'No special instructions were received'