Organocatalytic enantioselective α-difluoromethylketone thiolation of β-keto esters using phthalimide-SCF<sub>2</sub>COAr.
Chang, Wenning; Wang, En; Liang, Junqing; Shao, Xusheng; Xu, Xiaoyong; Yang, Wu-Lin; Li, Zhong; Organic & biomolecular chemistry 23 (2025) 5747–5752; doi:10.1039/d5ob00520e

data_7160554
_publ_section_title
;
 Organocatalytic enantioselective &#x3b1;-difluoromethylketone thiolation
 of &#x3b2;-keto esters using phthalimide-SCF<sub>2</sub>COAr.
;
_journal_issue                   24
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5747
_journal_page_last               5752
_journal_paper_doi               10.1039/d5ob00520e
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C32 H28 F2 O4 S'
_chemical_formula_sum            'C32 H28 F2 O4 S'
_chemical_formula_weight         546.60
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-05 deposited with the CCDC.	2025-05-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.0660(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.9024(2)
_cell_length_b                   12.6959(2)
_cell_length_c                   10.5735(2)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      54.916
_cell_measurement_theta_min      3.666
_cell_volume                     1319.20(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            18509
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.896
_diffrn_reflns_theta_min         3.665
_diffrn_source_current           3.57
_diffrn_source_power             0.2491146
_diffrn_source_voltage           69.78
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.993
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6340
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1347 before and 0.0674 after correction.
The Ratio of minimum to maximum transmission is 0.8444.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             572
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.234
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2038 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         4862
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0310
_refine_ls_R_factor_gt           0.0284
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0372P)^2^+0.2011P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0714
_refine_ls_wR_factor_ref         0.0724
_reflns_Friedel_coverage         0.864
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                4666
_reflns_number_total             4862
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00520e2.cif
_cod_data_source_block           250227cwn_4i
_cod_depositor_comments          'Adding full bibliography for 7160554.cif.'
_cod_database_code               7160554
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.849
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C25(H25), C27(H27), C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C24(H24A,H24B), C26(H26A,H26B), C28(H28A,H28B), C29(H29A,
 H29B), C31(H31A,H31B), C32(H32A,H32B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C14(H14), C15(H15), C16(H16), C18(H18),
 C19(H19), C20(H20), C21(H21)
;
_shelx_res_checksum              55366
_shelx_hkl_checksum              92991
_olex2_submission_special_instructions 'No special instructions were received'