Enantioselective CuH-Catalyzed Anti-Markovnikov Hydroamination of 1,1-Disubstituted Alkenes.
Zhu, Shaolin; Buchwald, Stephen L.; Journal of the American Chemical Society  (2014) 141029103858000–; doi:10.1021/ja509786v

data_4122853
_publ_section_title
;
 Enantioselective CuH-Catalyzed Anti-Markovnikov Hydroamination of
 1,1-Disubstituted Alkenes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141029103858000
_journal_paper_doi               10.1021/ja509786v
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_sum            'C34 H41 N O'
_chemical_formula_weight         479.68
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                86.470(2)
_cell_angle_beta                 83.0990(14)
_cell_angle_gamma                89.5329(17)
_cell_formula_units_Z            2
_cell_length_a                   6.7128(2)
_cell_length_b                   9.2273(4)
_cell_length_c                   22.4255(9)
_cell_measurement_reflns_used    9783
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.47
_cell_measurement_theta_min      3.98
_cell_volume                     1376.38(9)
_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 (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 0.994
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Bruker Smart APEX2 CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0371
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            9823
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.875
_diffrn_reflns_theta_min         1.988
_diffrn_source
'I\mS micro-focus sealed tube, multilayer optics'
_exptl_absorpt_coefficient_mu    0.517
_exptl_absorpt_correction_T_max  0.753261
_exptl_absorpt_correction_T_min  0.693433
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'TWINABS (Sheldrick, 2009)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.157
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.340
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.110
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
; 
 Flack x determined using 4205 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.00(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     654
_refine_ls_number_reflns         9823
_refine_ls_number_restraints     1095
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0309
_refine_ls_R_factor_gt           0.0305
_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^)+(0.0485P)^2^+0.2291P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0841
_reflns_Friedel_coverage         0.962
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                9694
_reflns_number_total             9823
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja509786v_si_003.cif
_cod_data_source_block           X14141_t5
_cod_database_code               4122853
_shelx_estimated_absorpt_t_min   0.844
_shelx_estimated_absorpt_t_max   0.945
_shelxl_version_number           2014-2
_shelx_res_checksum              52807
_shelx_hkl_checksum              72920