Synthetic and Mechanistic Study of the Catalytic Enantioselective Preparation of Primary β-Amino Ketones from Enones and a Fluorinated Gabriel Reagent
Avidan-Shlomovich, Shlomit; Ghosh, Harisadhan; Szpilman, Alex M.; ACS Catalysis 5 (2015) 336–; doi:10.1021/cs501744e

data_4512456
_publ_section_title
;
 Synthetic and Mechanistic Study of the Catalytic Enantioselective
 Preparation of Primary \b-Amino Ketones from Enones and a Fluorinated
 Gabriel Reagent
;
_journal_issue                   1
_journal_name_full               'ACS Catalysis'
_journal_page_first              336
_journal_paper_doi               10.1021/cs501744e
_journal_volume                  5
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H19 F4 N O4'
_chemical_formula_sum            'C22 H19 F4 N O4'
_chemical_formula_weight         437.38
_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_date             2014-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.878(17)
_cell_length_b                   15.68(2)
_cell_length_c                   19.97(3)
_cell_measurement_reflns_used    23
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      23.90
_cell_measurement_theta_min      7.23
_cell_volume                     4032(10)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    OLEX2
_computing_publication_material  OLEX2
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0306
_diffrn_reflns_av_unetI/netI     0.0159
_diffrn_reflns_Laue_measured_fraction_full 0.941
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            60446
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.077
_diffrn_reflns_theta_min         3.584
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.065
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.6559
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0833 before and 0.0466 after correction.
The Ratio of minimum to maximum transmission is 0.8712.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             1808
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.111
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 2896 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.010(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     567
_refine_ls_number_reflns         6804
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0238
_refine_ls_R_factor_gt           0.0233
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0334P)^2^+0.6721P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0603
_refine_ls_wR_factor_ref         0.0605
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    0.915
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                6701
_reflns_number_total             6804
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs501744e_si_002.cif
_cod_data_source_block           cu_ca200114_0m
_cod_depositor_comments          'Adding full bibliography for 4512456.cif.'
_cod_original_cell_volume        4033(10)
_cod_database_code               4512456
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C5(H5), C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C29(H29A,H29B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C16(H16), C17(H17), C25(H25), C26(H26), C38(H38), C39(H39)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C)
;