Enantioselective Synthesis of Hemiaminals via Pd-Catalyzed C-N Coupling with Chiral Bisphosphine Mono-oxides.
Li, Hongming; Belyk, Kevin M.; Yin, Jingjun; Chen, Qinghao; Hyde, Alan; Ji, Yining; Oliver, Steven; Tudge, Matthew T.; Campeau, Louis-Charles; Campos, Kevin R.; Journal of the American Chemical Society 137 (2015) 13728–13731; doi:10.1021/jacs.5b05934

data_4124726
_publ_section_title
;
 Enantioselective Synthesis of Hemiaminals via Pd-Catalyzed C-N Coupling
 with Chiral Bisphosphine Mono-oxides.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13728
_journal_page_last               13731
_journal_paper_doi               10.1021/jacs.5b05934
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H19 Cl2 N O'
_chemical_formula_sum            'C21 H19 Cl2 N O'
_chemical_formula_weight         372.27
_chemical_name_systematic
; 
(S)-3,10-dichloro-6-cyclohexyl-6H-benzo[5,6][1,3]oxazino[3,4-a]indole 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.5752(4)
_cell_length_b                   15.0262(10)
_cell_length_c                   21.0896(13)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.64
_cell_measurement_theta_min      2.94
_cell_volume                     1766.8(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0239
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            11648
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         66.632
_diffrn_reflns_theta_min         3.612
_diffrn_source                   'sealed-tube X-ray generator'
_exptl_absorpt_coefficient_mu    3.364
_exptl_absorpt_correction_T_max  0.60
_exptl_absorpt_correction_T_min  0.48
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
(SADABS; Sheldrick, 2003)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_description       cut
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.150
_exptl_transmission_factor_max   0.7528
_exptl_transmission_factor_min   0.6046
_refine_diff_density_max         0.138
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
; 
 Flack x determined using 1267 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.001(3)
_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     226
_refine_ls_number_reflns         3102
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0206
_refine_ls_R_factor_gt           0.0205
_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^)+(0.0276P)^2^+0.4704P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0533
_refine_ls_wR_factor_ref         0.0534
_reflns_Friedel_coverage         0.699
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                3091
_reflns_number_total             3102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b05934_si_004.cif
_cod_data_source_block           mdk046
_cod_depositor_comments
'Adding full bibliography for 4124726--4124727.cif.'
_cod_database_code               4124726
_shelx_estimated_absorpt_t_min   0.487
_shelx_estimated_absorpt_t_max   0.632