Organocatalytic asymmetric addition of alcohols to cyclic trifluoromethyl ketimines: highly enantioselective synthesis of chiral N,O-ketals.
Zhou, Ding; Yu, Xueting; Zhang, Jian; Wang, Wei; Xie, Hexin; Organic & biomolecular chemistry 14 (2016) 6193–6196; doi:10.1039/c6ob00890a

data_7155122
_publ_section_title
;
 Organocatalytic asymmetric addition of alcohols to cyclic trifluoromethyl
 ketimines: highly enantioselective synthesis of chiral N,O-ketals.
;
_journal_issue                   26
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6193
_journal_page_last               6196
_journal_paper_doi               10.1039/c6ob00890a
_journal_volume                  14
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C18 H16 Cl F3 N2 O3'
_chemical_formula_sum            'C18 H16 Cl F3 N2 O3'
_chemical_formula_weight         400.78
_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'
_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
_audit_creation_date             2014-11-17
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2016-04-26 deposited with the CCDC.
2016-05-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.5060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4639(6)
_cell_length_b                   18.9173(12)
_cell_length_c                   12.0648(8)
_cell_measurement_reflns_used    6060
_cell_measurement_temperature    130
_cell_measurement_theta_max      29.54
_cell_measurement_theta_min      2.46
_cell_volume                     2100.2(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21449
_diffrn_reflns_point_group_measured_fraction_full 0.841
_diffrn_reflns_point_group_measured_fraction_max 0.808
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.594
_diffrn_reflns_theta_min         2.043
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.226
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6844
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0537 before and 0.0413 after correction.
The Ratio of minimum to maximum transmission is 0.9173.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.163
_refine_diff_density_min         -0.448
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 2792 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         10461
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0665
_refine_ls_R_factor_gt           0.0564
_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^)+(0.1082P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1572
_refine_ls_wR_factor_ref         0.1661
_reflns_Friedel_coverage         0.579
_reflns_Friedel_fraction_full    0.672
_reflns_Friedel_fraction_max     0.609
_reflns_number_gt                8605
_reflns_number_total             10461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ob00890a2.cif
_cod_data_source_block           mo_dm14660_0m
_cod_depositor_comments          'Adding full bibliography for 7155122.cif.'
_cod_database_code               7155122
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.935
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C16A-O6
 1.48 with sigma of 0.01
3. Rigid bond restraints
 C12A, C13A, C13A, C14A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim O6 \\sim
C16A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C13A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(O6) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
5.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9A(H9AA,H9AB)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C6(H6), C7(H7), C11(H11), C12(H12), C14(H14), C15(H15),
 N3(H3), C4A(H4A), C6A(H6A), C7A(H7A), C11A(H11A), C12A(H12A), C14A(H14A),
 C15A(H15A)
5.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C16A(H16D,H16E,H16F), C18A(H18D,
 H18E,H18F)
;
_shelx_res_checksum              10364
_olex2_submission_special_instructions 'No special instructions were received'