Catalytic Asymmetric Construction of Halogenated Stereogenic Carbon Centers by Direct Vinylogous Mannich-Type Reaction.
Zhong, Feng; Yue, Wen-Jun; Zhang, Hai-Jun; Zhang, Cheng-Yuan; Yin, Liang; Journal of the American Chemical Society 140 (2018) 15170–15175; doi:10.1021/jacs.8b09484

data_4133307
_publ_section_title
;
 Catalytic Asymmetric Construction of Halogenated Stereogenic Carbon
 Centers by Direct Vinylogous Mannich-Type Reaction.
;
_journal_issue                   45
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15170
_journal_page_last               15175
_journal_paper_doi               10.1021/jacs.8b09484
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_sum            'C33 H40 Br N3 O3'
_chemical_formula_weight         606.59
_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
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 96.2370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5281(3)
_cell_length_b                   9.2306(2)
_cell_length_c                   30.7030(7)
_cell_measurement_reflns_used    9213
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      48.920
_cell_measurement_theta_min      4.671
_cell_volume                     3247.81(13)
_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-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0482
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            74521
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         2.336
_exptl_absorpt_coefficient_mu    1.301
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5620
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.241
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.120
_refine_diff_density_max         0.172
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
; 
 Flack x determined using 3514 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.003(4)
_refine_ls_extinction_coef       0.0038(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     736
_refine_ls_number_reflns         12659
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0614
_refine_ls_R_factor_gt           0.0337
_refine_ls_shift/su_max          0.019
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0241P)^2^+0.3724P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0654
_refine_ls_wR_factor_ref         0.0757
_reflns_Friedel_coverage         0.863
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                9320
_reflns_number_total             12659
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09484_si_004.cif
_cod_data_source_block           mo_d8v18355_0m
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4133307
_shelx_estimated_absorpt_t_min   0.781
_shelx_estimated_absorpt_t_max   0.860
_shelxl_version_number           2013-4
_shelx_res_checksum              98620
_shelx_hkl_checksum              43887