Asymmetric Cu-Catalyzed 1,4-Dearomatization of Pyridines and Pyridazines without Preactivation of the Heterocycle or Nucleophile.
Gribble, Jr, Michael W; Guo, Sheng; Buchwald, Stephen L.; Journal of the American Chemical Society 140 (2018) 5057–5060; doi:10.1021/jacs.8b02568

data_4132242
_publ_section_title
;
 Asymmetric Cu-Catalyzed 1,4-Dearomatization of Pyridines and Pyridazines
 without Preactivation of the Heterocycle or Nucleophile.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5057
_journal_page_last               5060
_journal_paper_doi               10.1021/jacs.8b02568
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_sum            'C19 H24 Cl N'
_chemical_formula_weight         301.84
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 91.6866(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.8999(9)
_cell_length_b                   5.6054(5)
_cell_length_c                   13.3076(11)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.41
_cell_measurement_theta_min      2.38
_cell_volume                     812.72(12)
_computing_cell_refinement       'SAINT 7.46A (Bruker-AXS, 2015)'
_computing_data_collection       'APEX2 v2011.4.0 (Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT 7.46A (Bruker-AXS, 2015)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2015 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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  0.0271
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            22862
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.990
_diffrn_reflns_theta_min         1.531
_diffrn_source
'I\mS micro-focus sealed tube, multilayer optics'
_exptl_absorpt_coefficient_mu    0.229
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       blade
_exptl_crystal_F_000             324
_exptl_crystal_size_max          0.700
_exptl_crystal_size_mid          0.165
_exptl_crystal_size_min          0.070
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
; 
 Flack x determined using 2110 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.005(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         5141
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0310
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0369P)^2^+0.1663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0727
_refine_ls_wR_factor_ref         0.0741
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                4933
_reflns_number_total             5141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02568_si_002.cif
_cod_data_source_block           X17111
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4132242
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.856
_shelx_estimated_absorpt_t_max   0.984
_shelx_res_checksum              91066
_shelx_hkl_checksum              31758