Thiourea fused γ-amino alcohol organocatalysts for asymmetric Mannich reaction of β-keto active methylene compounds with imines
Nomura, Miku; Begum, Zubeda; Seki, Chigusa; Okuyama, Yuko; Kwon, Eunsang; Uwai, Koji; Tokiwa, Michio; Tokiwa, Suguru; Takeshita, Mitsuhiro; Nakano, Hiroto; RSC Advances 13 (2023) 3715–3722; doi:10.1039/D2RA08317E

data_7246201
_publ_section_title
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 Thiourea fused \g-amino alcohol organocatalysts for asymmetric Mannich
 reaction of \b-keto active methylene compounds with imines
;
_journal_issue                   6
_journal_name_full               'RSC Advances'
_journal_page_first              3715
_journal_page_last               3722
_journal_paper_doi               10.1039/D2RA08317E
_journal_volume                  13
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H27 F6 N3 O S'
_chemical_formula_sum            'C28 H27 F6 N3 O S'
_chemical_formula_weight         567.58
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-14
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-06-14 deposited with the CCDC.	2023-01-19 downloaded from the CCDC.
;
_cell_angle_alpha                98.031(6)
_cell_angle_beta                 98.938(6)
_cell_angle_gamma                90.963(6)
_cell_formula_units_Z            2
_cell_length_a                   9.2836(7)
_cell_length_b                   10.9381(7)
_cell_length_c                   13.6479(10)
_cell_measurement_reflns_used    4831
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      66.79
_cell_measurement_theta_min      3.31
_cell_volume                     1354.57(17)
_computing_cell_refinement       'SAINT V8.40B (Bruker AXS Inc., 2017)'
_computing_data_collection
'Bruker Instrument Service V8.5.0 (Bruker AXS Inc., 2021)'
_computing_data_reduction        'SAINT V8.40B (Bruker AXS Inc., 2017)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT V2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(1)
_diffrn_detector_area_resol_mean 7.37
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1467
_diffrn_reflns_av_unetI/netI     0.1511
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15416
_diffrn_reflns_point_group_measured_fraction_full 0.887
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.981
_diffrn_reflns_theta_min         3.312
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.671
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.4809
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1239 before and 0.0887 after correction.
The Ratio of minimum to maximum transmission is 0.6388.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       needle
_exptl_crystal_F_000             588
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.552
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 1762 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.10(3)
_refine_ls_extinction_coef       0.0009(7)
_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   0.998
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     716
_refine_ls_number_reflns         8669
_refine_ls_number_restraints     519
_refine_ls_restrained_S_all      0.988
_refine_ls_R_factor_all          0.1264
_refine_ls_R_factor_gt           0.0826
_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^)+(0.0970P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1954
_refine_ls_wR_factor_ref         0.2257
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.796
_reflns_Friedel_fraction_max     0.806
_reflns_number_gt                5535
_reflns_number_total             8669
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra08317e2.cif
_cod_data_source_block           p1_a
_cod_database_code               7246201
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.764
_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 O(H) groups
2. Restrained distances
 N1-H1
 0.9 with sigma of 0.02
 N00B-H00B
 0.9 with sigma of 0.02
 N00G-H00G
 0.9 with sigma of 0.02
 N00H-H00H
 0.9 with sigma of 0.02
 C00U-H1
 1.87 with sigma of 0.04
 C01U-H1
 1.82 with sigma of 0.04
 C01H-H00B
 1.8 with sigma of 0.04
 C01S-H00B
 1.85 with sigma of 0.04
 C00O-H00G
 1.91 with sigma of 0.04
 C01U-H00G
 1.82 with sigma of 0.04
 C00X-H00H
 1.93 with sigma of 0.04
 C01H-H00H
 1.83 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4.a Ternary CH refined with riding coordinates:
 C00O(H00O), C00X(H00X)
4.b Secondary CH2 refined with riding coordinates:
 C012(H01L,H01M), C015(H01A,H01B), C018(H01C,H01D), C01D(H01S,H01T), C01E(H01E,
 H01F), C01J(H01G,H01H), C01L(H01U,H01V), C01M(H01W,H01X), C01Q(H01J,H01K),
 C020(H02A,H02B)
4.c Aromatic/amide H refined with riding coordinates:
 C00P(H00P), C00R(H00R), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011),
 C013(H013), C016(H016), C019(H019), C01A(H01O), C01B(H01P), C01C(H01Q),
 C01I(H01I), C01N(H01N), C01O(H01), C01P(H3), C01R(H01R), C01W(H4), C01X(H5),
 C01Y(H01Y), C01Z(H01Z), C021(H021), C023(H023), C024(H024), C025(H025),
 C026(H026)
4.d Tetrahedral OH refined with riding coordinates:
 O2(H2), O1(H1A)
;
_shelx_res_checksum              14103
_olex2_submission_special_instructions 'No special instructions were received'