A direct approach to amines with remote stereocenters by enantioselective CuH-catalysed reductive relay hydroamination
Shaolin Zhu; Nootaree Niljianskul; Stephen L. Buchwald; Nature Chemistry 8 (2016) 144–150; doi:10.1038/nchem.2418

data_1548529
_publ_section_title
;
 A direct approach to amines with remote stereocenters by enantioselective
 CuH-catalysed reductive relay hydroamination
;
_journal_name_full               'Nature Chemistry'
_journal_page_first              144
_journal_page_last               150
_journal_paper_doi               10.1038/nchem.2418
_journal_volume                  8
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_sum            'C22 H31 Cl2 N'
_chemical_formula_weight         380.38
_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     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 102.4250(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.7424(5)
_cell_length_b                   17.1958(14)
_cell_length_c                   9.2973(7)
_cell_measurement_reflns_used    9854
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.80
_cell_measurement_theta_min      2.37
_cell_volume                     1052.69(14)
_computing_cell_refinement       'SAINT 7.46A (Bruker-AXS, 2011)'
_computing_data_collection       'APEX2 v2011.4.0 (Bruker-AXS, 2011)'
_computing_data_reduction        'SAINT 7.46A (Bruker-AXS, 2011)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker Smart APEX2 CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            39501
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.027
_diffrn_reflns_theta_min         2.243
_diffrn_source
'I\mS micro-focus sealed tube, multilayer optics'
_exptl_absorpt_coefficient_mu    0.313
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       blade
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.450
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
; 
 Flack x determined using 3093 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.010(14)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         7166
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0351
_refine_ls_R_factor_gt           0.0321
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0458P)^2^+0.1124P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0821
_reflns_Friedel_coverage         0.934
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                6740
_reflns_number_total             7166
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2418-s2.cif
_cod_data_source_block           X15053
_cod_database_code               1548529
_shelx_estimated_absorpt_t_min   0.872
_shelx_estimated_absorpt_t_max   0.977
_shelxl_version_number           2014/6
_shelx_res_checksum              10681
_shelx_hkl_checksum              39635