Enantioselective Synthesis of Calix[4]arenes with C–C Axial and Inherent Chirality via Palladium/Chiral Norbornene Cooperative Catalysis
You, Yiming; Cheng, Hongwei; Huang, Xiao; Wang, Peng; Cong, Hengjiang; Cheng, Hong-Gang; Zhou, Qianghui; Chemical Science  (2026) –; doi:10.1039/D5SC10040B

data_1576775
_publ_section_title
;
 Enantioselective synthesis of calix[4]arenes with C-C axial and inherent
 chirality <i>via</i> palladium/chiral norbornene cooperative catalysis.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              8968
_journal_page_last               8975
_journal_paper_doi               10.1039/d5sc10040b
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C69 H65 O6 P, C H Cl3'
_chemical_formula_sum            'C70 H66 Cl3 O6 P'
_chemical_formula_weight         1140.54
_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             2024-11-16
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-11-19 deposited with the CCDC.	2026-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.001(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.6469(4)
_cell_length_b                   20.7272(6)
_cell_length_c                   13.9592(4)
_cell_measurement_reflns_used    9599
_cell_measurement_temperature    298.6(6)
_cell_measurement_theta_max      73.7310
_cell_measurement_theta_min      4.5190
_cell_volume                     3146.01(18)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 40.35a 64-bit (release 18-12-2018))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.6(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -49.00 -10.00   0.50   15.00    --  -46.60  71.00 105.00   78
  2  \w    -92.00 -66.00   0.50   15.00    --  -46.60 -71.00 -24.00   52
  3  \w     -3.00  33.00   0.50   15.00    --  -46.60  71.00 105.00   72
  4  \w    -91.00 -60.00   0.50   50.00    -- -104.60  71.00 105.00   62
  5  \w   -124.00 -97.00   0.50   50.00    -- -104.60 -71.00 -24.00   54
  6  \w   -193.00-146.00   0.50   50.00    -- -104.60 -71.00 -24.00   94
  7  \w    -45.00 -20.00   0.50   15.00    --    5.00 -71.00 -24.00   50
  8  \w      7.00  32.00   0.50   15.00    --    5.00  71.00 105.00   50
  9  \w    -84.00  35.00   0.50   15.00    --    5.00 -75.00 -90.00  238
 10  \w    -77.00  43.00   0.50   15.00    --  -46.60  57.00  60.00  240
 11  \w    -65.00 -32.00   0.50   15.00    --  -46.60 -57.00   0.00   66
 12  \w   -136.00  42.00   0.50   15.00    --  -46.60   0.00  60.00  356
 13  \w   -194.00 -70.00   0.50   50.00    -- -104.60 -57.00 -60.00  248
 14  \w   -193.00 -66.00   0.50   50.00    -- -104.60 -38.00-150.00  254
 15  \w   -174.00 -65.00   0.50   50.00    -- -104.60 -38.00-120.00  218
 16  \w   -101.00 -75.00   0.50   50.00    -- -104.60  57.00  30.00   52
 17  \w    -47.00 -17.00   0.50   50.00    -- -104.60  57.00  30.00   60
 18  \w    -92.00 -66.00   0.50   50.00    -- -104.60 -75.00 120.00   52
 19  \w   -194.00 -70.00   0.50   50.00    -- -104.60 -57.00  30.00  248
 20  \w   -194.00-125.00   0.50   50.00    -- -104.60 -57.00   0.00  138
 21  \w    -92.00 -29.00   0.50   50.00    -- -104.60  75.00  90.00  126
 22  \w   -170.00-130.00   0.50   50.00    -- -104.60 -75.00 120.00   80
 23  \w   -145.00-106.00   0.50   50.00    -- -104.60  75.00  90.00   78
 24  \w   -115.00 -72.00   0.50   50.00    -- -104.60 -57.00   0.00   86
 25  \w   -192.00-149.00   0.50   50.00    -- -104.60 -75.00-120.00   86
 26  \w   -108.00 -83.00   0.50   50.00    -- -104.60 -75.00-120.00   50
 27  \w   -142.00-117.00   0.50   50.00    -- -104.60  75.00-150.00   50
 28  \w    -42.00 -15.00   0.50   50.00    -- -104.60  75.00-150.00   54
 29  \w   -192.00 -89.00   0.50   50.00    -- -104.60 -57.00  60.00  206
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0083896000
_diffrn_orient_matrix_UB_12      0.0433969000
_diffrn_orient_matrix_UB_13      -0.0869154000
_diffrn_orient_matrix_UB_21      0.1071354000
_diffrn_orient_matrix_UB_22      0.0374178000
_diffrn_orient_matrix_UB_23      0.0782106000
_diffrn_orient_matrix_UB_31      0.0924091000
_diffrn_orient_matrix_UB_32      -0.0472378000
_diffrn_orient_matrix_UB_33      -0.0177942000
_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  0.0415
_diffrn_reflns_av_unetI/netI     0.0459
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            35174
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.483
_diffrn_reflns_theta_max         67.483
_diffrn_reflns_theta_min         3.391
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.956
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55188
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.204
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.933
_refine_diff_density_min         -0.727
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 3791 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.036(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     701
_refine_ls_number_reflns         11298
_refine_ls_number_restraints     148
_refine_ls_restrained_S_all      1.223
_refine_ls_R_factor_all          0.0955
_refine_ls_R_factor_gt           0.0867
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2450
_refine_ls_wR_factor_ref         0.2604
_reflns_Friedel_coverage         0.937
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                9401
_reflns_number_total             11298
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc10040b2.cif
_cod_data_source_block           yym-6-asy
_cod_depositor_comments          'Adding full bibliography for 1576775.cif.'
_cod_database_code               1576775
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         CHOP
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.909
_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. Restrained distances
 O1-C35
 1.5 with sigma of 0.02
 C43-C42
 1.5 with sigma of 0.02
 C39-C38
 1.5 with sigma of 0.02
 C40-C39
 1.5 with sigma of 0.02
 C42-C41
 1.5 with sigma of 0.02
 C36-C37
 1.5 with sigma of 0.02
 C45-C44
 1.5 with sigma of 0.01
 C46-C45
 1.5 with sigma of 0.01
 C36-C35
 1.5 with sigma of 0.01
 Cl2-Cl1 \\sim Cl2-Cl3 \\sim Cl3-Cl1
 with sigma of 0.01
 Cl2-C69 \\sim Cl3-C69 \\sim Cl1-C69
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O3 \\sim C41 \\sim C42 \\sim C43: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O4 \\sim C44 \\sim C45: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C40 \\sim C39 \\sim C38 \\sim O2: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C46 \\sim C45 \\sim C44 \\sim O4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Cl3 \\sim C69 \\sim Cl2 \\sim Cl1: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C64 \\sim C63 \\sim C68 \\sim C67 \\sim C66 \\sim C65: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Cl3 \\sim Cl1 \\sim C69 \\sim Cl2: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Cl2 \\sim Cl3 \\sim C69 \\sim Cl1: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C37 \\sim C36 \\sim C35 \\sim O1: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
O1 \\sim C35 \\sim C36 \\sim C37: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
Uanis(Cl3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C69(H69)
4.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C34(H34A,H34B), C7(H7A,H7B), C27(H27A,H27B), C38(H38A,H38B),
 C41(H41A,H41B), C39(H39A,H39B), C44(H44A,H44B), C42(H42A,H42B), C45(H45A,H45B),
  C35(H35A,H35B), C36(H36A,H36B)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C18(H18), C31(H31), C29(H29), C58(H58), C50(H50), C30(H30), C4(H4),
 C3(H3), C2(H2), C55(H55), C52(H52), C49(H49), C22(H22), C13(H13), C24(H24),
 C12(H12), C59(H59), C23(H23), C53(H53), C62(H62), C54(H54), C61(H61), C64(H64),
  C65(H65), C66(H66), C67(H67), C68(H68), C60(H60)
4.d Fitted hexagon refined as free rotating group:
 C1(C6,C5,C4,C3,C2), C64(C65,C66,C67,C68,C63)
4.e Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C40(H40A,H40B,H40C), C37(H37A,H37B,H37C), C46(H46A,H46B,
 H46C)
;
_shelx_res_checksum              40871
_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 2.971
_oxdiff_exptl_absorpt_empirical_full_min 0.401