Ni-Catalyzed Enantioselective Intermolecular Hydroamination of Branched 1,3-Dienes Using Primary Aliphatic Amines.
Tran, Gaël; Shao, Wen; Mazet, Clément; Journal of the American Chemical Society 141 (2019) 14814–14822; doi:10.1021/jacs.9b07253

data_4127635
_publ_section_title
;
 Ni-Catalyzed Enantioselective Intermolecular Hydroamination of Branched
 1,3-Dienes Using Primary Aliphatic Amines.
;
_journal_issue                   37
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14814
_journal_page_last               14822
_journal_paper_doi               10.1021/jacs.9b07253
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Cl, C23 H24 N'
_chemical_formula_sum            'C23 H24 Cl N'
_chemical_formula_weight         349.88
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0457(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.48643(15)
_cell_length_b                   7.50634(11)
_cell_length_c                   12.56284(19)
_cell_measurement_reflns_used    9729
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      70.6480
_cell_measurement_theta_min      5.4140
_cell_volume                     988.72(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_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_environment      N~2~
_diffrn_ambient_temperature      180.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4670
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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    -65.00  12.00   0.50    1.00    --  -41.64  38.00-180.00  154
  2  \w   -113.00 -42.00   0.50    1.00    --  -41.64 -57.00  90.00  142
  3  \w    -69.00  24.00   0.50    1.00    --  -41.64  57.00-120.00  186
  4  \w      2.00  74.00   0.50    1.00    --   41.64 -99.00   0.00  144
  5  \w     29.00 106.00   0.50    1.00    --  100.00 -45.00-150.00  154
  6  \w     75.00 168.00   0.50    1.00    --  100.00  45.00  30.00  186
  7  \w    140.00 167.00   0.50    1.00    --  100.00  84.00 -87.00   54
  8  \w     72.00 163.00   0.50    1.00    --  100.00  61.00 -30.00  182
  9  \w     37.00 108.00   0.50    1.00    --  100.00-125.00 120.00  142
 10  \w    134.00 172.00   0.50    1.00    --  100.00  61.00-180.00   76
 11  \w    131.00 172.00   0.50    1.00    --  100.00 125.00 120.00   82
 12  \w     78.00 158.00   0.50    1.00    --  100.00  61.00-120.00  160
 13  \w    114.00 164.00   0.50    1.00    --  100.00 125.00-120.00  100
 14  \w     46.00 118.00   0.50    1.00    --  100.00-125.00-150.00  144
 15  \w     32.00  89.00   0.50    1.00    --  100.00 -94.00-150.00  114
 16  \w    141.00 171.00   0.50    1.00    --  100.00  61.00   0.00   60
 17  \w     73.00 100.00   0.50    1.00    --  100.00-125.00 -60.00   54
 18  \w     98.00 124.00   0.50    1.00    --  100.00 125.00 -90.00   52
 19  \w     99.00 137.00   0.50    1.00    --  100.00  84.00 -87.00   76
 20  \w   -112.00  -6.00   0.50    1.00    --  -41.64 -19.00 120.00  212
 21  \w     14.00  67.00   0.50    1.00    --   41.64  57.00 -60.00  106
 22  \w     12.00  38.00   0.50    1.00    --   46.00  82.00  17.08   52
 23  \w     11.00  37.00   0.50    1.00    --   46.00  84.00 115.40   52
 24  \w     16.00  43.00   0.50    1.00    --   50.00  82.00-157.80   54
 25  \w     16.00  41.00   0.50    1.00    --   50.00  81.00 -86.05   50
 26  \w     31.00  58.00   0.50    1.00    --   62.00  75.00  96.93   54
 27  \w     30.00  67.00   0.50    1.00    --   62.00  75.00 -75.47   74
 28  \w     33.00  79.00   0.50    1.00    --   66.00  77.00 -10.41   92
 29  \w     35.00  61.00   0.50    1.00    --   66.00  77.00-135.88   52
 30  \w     34.00  67.00   0.50    1.00    --   66.00  77.00  35.78   66
 31  \w     34.00  61.00   0.50    1.00    --   66.00  76.00 138.06   54
 32  \w     43.00  68.00   0.50    1.00    --   74.00  75.00 -52.28   50
 33  \w     92.00 145.00   0.50    1.00    --   74.00  77.00-172.03  106
 34  \w     41.00  67.00   0.50    1.00    --   74.00  77.00 100.99   52
 35  \w     44.00  72.00   0.50    1.00    --   74.00  77.00-172.03   56
 36  \w     43.00  69.00   0.50    1.00    --   74.00  76.00 156.26   52
 37  \w     68.00  93.00   0.50    1.00    --  100.00  77.00 -60.00   50
 38  \w    106.00 133.00   0.50    1.00    --  100.00  77.00  30.00   54
 39  \w     68.00  93.00   0.50    1.00    --  100.00  77.00  30.00   50
 40  \w    100.00 167.00   0.50    1.00    --  100.00  77.00 150.00  134
 41  \w    111.00 141.00   0.50    1.00    --  100.00  77.00-150.00   60
 42  \w     68.00  93.00   0.50    1.00    --  100.00  77.00-150.00   50
 43  \w     67.00  93.00   0.50    1.00    --  100.00  77.00 150.00   52
 44  \w     67.00  94.00   0.50    1.00    --  100.00  77.00 -30.00   54
 45  \w     67.00  94.00   0.50    1.00    --  100.00  77.00-120.00   54
 46  \w     68.00 164.00   0.50    1.00    --  100.00  77.00 120.00  192
 47  \w    138.00 166.00   0.50    1.00    --  100.00 125.00 150.00   56
 48  \w    100.00 176.00   0.50    1.00    --  100.00  77.00  90.00  152
 49  \w     67.00 122.00   0.50    1.00    --  100.00  77.00-180.00  110
 50  \w     67.00  95.00   0.50    1.00    --  100.00  77.00  90.00   56
 51  \w     67.00  93.00   0.50    1.00    --  100.00  77.00   0.00   52
 52  \w     68.00 144.00   0.50    1.00    --  100.00  77.00  60.00  152
 53  \w     67.00 117.00   0.50    1.00    --  100.00  77.00 -90.00  100
 54  \w     79.00 118.00   0.50    1.00    --  100.00-125.00 -30.00   78
 55  \w     67.00 118.00   0.50    1.00    --  100.00-125.00  30.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0439820000
_diffrn_orient_matrix_UB_12      -0.1523821000
_diffrn_orient_matrix_UB_13      0.0728031000
_diffrn_orient_matrix_UB_21      -0.0586211000
_diffrn_orient_matrix_UB_22      -0.0971536000
_diffrn_orient_matrix_UB_23      -0.0972852000
_diffrn_orient_matrix_UB_31      0.1273110000
_diffrn_orient_matrix_UB_32      -0.0972538000
_diffrn_orient_matrix_UB_33      -0.0169543000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15843
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.551
_diffrn_reflns_theta_min         3.519
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.719
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.393
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.175
_exptl_crystal_description       needle
_exptl_crystal_F_000             372
_exptl_crystal_size_max          0.957
_exptl_crystal_size_mid          0.155
_exptl_crystal_size_min          0.076
_refine_diff_density_max         0.132
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
 When determined using the quotient method ( 1589 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).) the Flack parameter is -0.019(7)
;
_refine_ls_abs_structure_Flack   -0.012(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3737
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0466P)^2^+0.0935P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0705
_refine_ls_wR_factor_ref         0.0718
_reflns_Friedel_coverage         0.835
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                3614
_reflns_number_total             3737
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07253_si_003.cif
_cod_data_source_block           ws3b
_cod_original_cell_volume        988.72(2)
_cod_database_code               4127635
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H24 N Cl'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.012(13)
 -0.012(13)
2. 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
3.a Ternary CH refined with riding coordinates:
 C15(H15)
3.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
3.d X=CH2 refined with riding coordinates:
 C14(H14A,H14B)
3.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              17939
_shelx_hkl_checksum              57015
_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 3.501
_oxdiff_exptl_absorpt_empirical_full_min 0.756