α-Halo Amides as Competent Latent Enolates: Direct Catalytic Asymmetric Mannich-Type Reaction.
Sun, Bo; Balaji, Pandur Venkatesan; Kumagai, Naoya; Shibasaki, Masakatsu; Journal of the American Chemical Society 139 (2017) 8295–8301; doi:10.1021/jacs.7b03291

data_4126206
_publ_section_title
;
 \a-Halo Amides as Competent Latent Enolates: Direct Catalytic Asymmetric
 Mannich-Type Reaction.
;
_journal_issue                   24
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8295
_journal_page_last               8301
_journal_paper_doi               10.1021/jacs.7b03291
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_formula_moiety         'C21 H22 Cl3 N3 O3'
_chemical_formula_sum            'C21 H22 Cl3 N3 O3'
_chemical_formula_weight         470.78
_space_group_crystal_system      hexagonal
_space_group_IT_number           173
_space_group_name_Hall           'P 6c'
_space_group_name_H-M_alt        'P 63'
_symmetry_space_group_name_Hall  'P 6c'
_symmetry_space_group_name_H-M   'P 63'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                120.0000
_cell_formula_units_Z            6
_cell_length_a                   19.4252(6)
_cell_length_b                   19.4252(6)
_cell_length_c                   12.1355(4)
_cell_measurement_reflns_used    29982
_cell_measurement_temperature    93
_cell_measurement_theta_max      68.23
_cell_measurement_theta_min      3.64
_cell_volume                     3965.7(2)
_computing_cell_refinement       'RAPID AUTO'
_computing_data_collection       'RAPID AUTO (Rigaku, ????)'
_computing_data_reduction        'RAPID AUTO'
_computing_molecular_graphics    'CrystalStructure 4.2.2'
_computing_publication_material  'CrystalStructure 4.2.2 (Rigaku, 2016)'
_computing_structure_refinement  'SHELXL Version 2014/7 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      93
_diffrn_detector_area_resol_mean 10.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       \w
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0802
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            46288
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.234
_diffrn_reflns_theta_min         4.493
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.337
_exptl_absorpt_correction_T_max  0.716
_exptl_absorpt_correction_T_min  0.475
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1464.00
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.28
_refine_diff_density_min         -0.21
_refine_ls_abs_structure_details
;
 Flack x determined using 1741 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4838
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0450
_refine_ls_shift/su_max          0.026
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[\s^2^(Fo^2^)+(0.0593P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.895
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                4351
_reflns_number_total             4838
_reflns_threshold_expression     F^2^>2.0\s(F^2^)
_cod_data_source_file            ja7b03291_si_006.cif
_cod_data_source_block           160920SunBo
_cod_depositor_comments
'Adding full bibliography for 4126206--4126208.cif.'
_cod_database_code               4126206
_shelx_res_checksum              17663
_shelx_hkl_checksum              48447
_platon_squeeze_void_probe_radius 1.20
_shelx_fab_checksum              75516