Catalytic Asymmetric Synthesis of Secondary Nitriles via Stereoconvergent Negishi Arylations and Alkenylations of Racemic α-Bromonitriles
Junwon Choi; Gregory C. Fu; Journal of the American Chemical Society 134 (2012) 9102–9105; doi:10.1021/ja303442q

data_4118028
_publ_section_title
;
 Catalytic Asymmetric Synthesis of Secondary Nitriles via Stereoconvergent
 Negishi Arylations and Alkenylations of Racemic \a-Bromonitriles
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9102
_journal_page_last               9105
_journal_paper_doi               10.1021/ja303442q
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_sum            'C20 H23 N O'
_chemical_formula_weight         293.39
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 104.760(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            16
_cell_length_a                   14.4823(5)
_cell_length_b                   32.2596(10)
_cell_length_c                   14.5199(5)
_cell_measurement_reflns_used    9508
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.82
_cell_measurement_theta_min      3.43
_cell_volume                     6559.7(4)
_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-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker Smart APEX2 CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Incoatech ImuS multilayer optics'
_diffrn_radiation_source         'ImuS micro-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_sigmaI/netI    0.0186
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            196268
_diffrn_reflns_theta_full        68.22
_diffrn_reflns_theta_max         68.22
_diffrn_reflns_theta_min         1.37
_exptl_absorpt_coefficient_mu    0.559
_exptl_absorpt_correction_T_max  0.9567
_exptl_absorpt_correction_T_min  0.8503
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.188
_exptl_crystal_description       needle
_exptl_crystal_F_000             2528
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.06(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1676
_refine_ls_number_reflns         23690
_refine_ls_number_restraints     1932
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0421
_refine_ls_R_factor_gt           0.0405
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0652P)^2^+0.9823P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1032
_refine_ls_wR_factor_ref         0.1066
_reflns_number_gt                22997
_reflns_number_total             23690
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja303442q_si_002.cif
_cod_data_source_block           x12022
_cod_database_code               4118028