Enantioselective Synthesis of N-Arylpyrrole Aldehydes via NHC-Organocatalytic Atroposelective Desymmetrization Followed by Kinetic Resolution
Hu, Chunyang; Liu, Zuquan; Li, Chenxing; Feng, Jianquan; Zhu, Yiwei; Du, Ding; Chemical Communications  (2026) –; doi:10.1039/D5CC06389B

data_7135335
_publ_section_title
;
 Enantioselective Synthesis of N-Arylpyrrole Aldehydes via
 NHC-Organocatalytic Atroposelective Desymmetrization Followed by Kinetic
 Resolution
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC06389B
_journal_year                    2026
_chemical_formula_moiety         'C24 H23 N3 O3 S'
_chemical_formula_sum            'C24 H23 N3 O3 S'
_chemical_formula_weight         433.51
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-30
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2025-09-18 deposited with the CCDC.	2025-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.6279(17)
_cell_length_b                   7.9727(4)
_cell_length_c                   15.4012(7)
_cell_measurement_reflns_used    10152
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      78.2790
_cell_measurement_theta_min      2.4520
_cell_volume                     4374.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.938
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -117.00 -91.00   0.50    0.50    -- -105.00 -38.00 -30.00   52
  2  \w   -174.00-138.00   0.50    0.50    -- -105.00 -38.00 -30.00   72
  3  \w   -127.00-101.00   0.50    0.50    -- -105.00 -28.00 -99.00   52
  4  \w   -114.00 -44.00   0.50    0.16    --  -47.33 -28.00 -99.00  140
  5  \w    -65.00 -39.00   0.50    0.50    -- -105.00  57.00   0.00   52
  6  \w    -65.00 -40.00   0.50    0.50    -- -105.00  57.00  60.00   50
  7  \w    -61.00 -35.00   0.50    0.50    -- -105.00  57.00 150.00   52
  8  \w    -64.00 -39.00   0.50    0.50    -- -105.00  57.00 -30.00   50
  9  \w    -64.00 -33.00   0.50    0.50    -- -105.00  57.00 -90.00   62
 10  \w    -64.00 -33.00   0.50    0.50    -- -105.00  57.00 -60.00   62
 11  \w    -65.00 -34.00   0.50    0.50    -- -105.00  57.00-120.00   62
 12  \w    -62.00 -32.00   0.50    0.50    -- -105.00  57.00-150.00   60
 13  \w    -66.00 -41.00   0.50    0.50    -- -105.00  57.00-180.00   50
 14  \w   -105.00 -55.00   0.50    0.50    -- -105.00  77.00-150.00  100
 15  \w    -29.00  18.00   0.50    0.16    --  -47.33  38.00-150.00   94
 16  \w    -40.00  26.00   0.50    0.16    --  -47.33  38.00-180.00  132
 17  \w    -24.00  19.00   0.50    0.16    --  -47.33  28.00  62.00   86
 18  \w     34.00 122.00   0.50    0.16    --   47.33  28.00  62.00  176
 19  \w    103.00 128.00   0.50    0.50    --  112.48  57.00 150.00   50
 20  \w    101.00 176.00   0.50    0.50    --  112.48  38.00 150.00  150
 21  \w    151.00 176.00   0.50    0.50    --  112.48  57.00 150.00   50
 22  \w     98.00 171.00   0.50    0.50    --  112.48  28.00  62.00  146
 23  \w      3.00  28.00   0.50    0.16    --   47.33 -28.00 -99.00   50
 24  \w     71.00  99.00   0.50    0.50    --  112.48 -77.00   0.00   56
 25  \w     54.00  80.00   0.50    0.50    --  112.48-125.00 120.00   52
 26  \w     85.00 110.00   0.50    0.50    --  112.48-125.00 120.00   50
 27  \w     43.00 100.00   0.50    0.50    --  112.48 -99.00 120.00  114
 28  \w   -117.00 -65.00   0.50    0.16    --  -46.65 178.00 -60.00  104
 29  \w    -68.00  -7.00   0.50    0.16    --  -46.65  77.00-150.00  122
 30  \w     87.00 113.00   0.50    0.16    --   46.65 178.00 120.00   52
 31  \w   -113.00 -94.00   0.50    0.50    -- -105.00-125.00 -60.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0090115000
_diffrn_orient_matrix_UB_12      0.0398954000
_diffrn_orient_matrix_UB_13      -0.0722673000
_diffrn_orient_matrix_UB_21      -0.0994151000
_diffrn_orient_matrix_UB_22      -0.0026451000
_diffrn_orient_matrix_UB_23      0.0171604000
_diffrn_orient_matrix_UB_31      0.0059853000
_diffrn_orient_matrix_UB_32      0.0165075000
_diffrn_orient_matrix_UB_33      0.1783672000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1076
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            27910
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         81.764
_diffrn_reflns_theta_min         5.687
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.568
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49740
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       block
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.421
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.060
_refine_ls_extinction_coef       0.00040(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.205
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     288
_refine_ls_number_reflns         4550
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.205
_refine_ls_R_factor_all          0.1444
_refine_ls_R_factor_gt           0.1043
_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^)+(0.0290P)^2^+12.2264P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2051
_refine_ls_wR_factor_ref         0.2229
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2954
_reflns_number_total             4550
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06389b2.cif
_cod_data_source_block           1
_cod_database_code               7135335
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         chno
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(2)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(2)
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=1-FVAR(3)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(3)
3.a Aromatic/amide H refined with riding coordinates:
 N003(H003), C17(H17), C2(H2), C11(H11), C20(H20), C12(H12), C5(H5), C3(H3),
 C4(H4), C21(H21), C14(H14)
3.b Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C),
 C10A(H10D,H10E,H10F), C9A(H9AA,H9AB,H9AC), C8A(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              33678
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.562
_oxdiff_exptl_absorpt_empirical_full_min 0.546