<i>De novo</i> synthesis of inherently chiral heteracalix[4]aromatics from enantioselective macrocyclization enabled by chiral phosphoric acid-catalyzed intramolecular S<sub>N</sub>Ar reaction.
Li, Xing-Chi; Cheng, Ying; Wang, Xu-Dong; Tong, Shuo; Wang, Mei-Xiang; Chemical science 15 (2024) 3610–3615; doi:10.1039/d3sc06436k

data_1571358
_publ_section_title
;
 <i>De novo</i> synthesis of inherently chiral heteracalix[4]aromatics
 from enantioselective macrocyclization enabled by chiral phosphoric
 acid-catalyzed intramolecular S<sub>N</sub>Ar reaction.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              3610
_journal_page_last               3615
_journal_paper_doi               10.1039/d3sc06436k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C40 H40 Br N9 O4'
_chemical_formula_sum            'C40 H40 Br N9 O4'
_chemical_formula_weight         790.72
_chemical_name_systematic        lxc-200-3
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-10-27 deposited with the CCDC.	2024-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                74.250(2)
_cell_angle_beta                 73.2240(10)
_cell_angle_gamma                70.731(2)
_cell_formula_units_Z            2
_cell_length_a                   11.19970(10)
_cell_length_b                   11.6776(2)
_cell_length_c                   15.8142(3)
_cell_measurement_reflns_used    62369
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.8410
_cell_measurement_theta_min      4.0710
_cell_volume                     1833.45(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.957
_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     34.00 122.00   0.50    0.05    --   46.63  17.00 131.00  176
  2  \w     26.00 122.00   0.50    0.05    --   50.00  79.00  12.99  192
  3  \w     34.00 120.00   0.50    0.05    --   46.63  37.00   0.00  172
  4  \w     34.00 120.00   0.50    0.05    --   46.63  37.00-180.00  172
  5  \w     30.00 126.00   0.50    0.05    --   54.00  80.00 -51.56  192
  6  \w     48.00 143.00   0.50    0.05    --   70.00  75.00 -35.50  190
  7  \w     30.00 126.00   0.50    0.05    --   54.00  79.00  59.09  192
  8  \w     31.00 126.00   0.50    0.05    --   54.00  77.00  93.84  190
  9  \w     37.00 131.00   0.50    0.05    --   58.00  73.00 125.19  188
 10  \w     44.00 139.00   0.50    0.05    --   66.00  76.00  67.61  190
 11  \w     92.00 178.00   0.50    0.05    --  104.75  17.00 131.00  172
 12  \w     42.00 135.00   0.50    0.05    --   62.00  70.00  63.88  186
 13  \w     42.00 135.00   0.50    0.05    --   62.00  70.00  30.89  186
 14  \w     83.00 108.00   0.50    0.05    --  104.75 -77.00 -30.00   50
 15  \w     34.00  62.00   0.50    0.05    --  104.75 -61.00 -90.00   56
 16  \w     35.00  65.00   0.50    0.05    --  104.75 -77.00 -30.00   60
 17  \w     35.00  72.00   0.50    0.05    --  104.75 -61.00 -30.00   74
 18  \w     32.00  59.00   0.50    0.05    --  104.75 -77.00 150.00   54
 19  \w     82.00 108.00   0.50    0.05    --  104.75 -77.00 150.00   52
 20  \w     62.00 105.00   0.50    0.05    --  104.75 -77.00 120.00   86
 21  \w     33.00 106.00   0.50    0.05    --  104.75 -94.00  60.00  146
 22  \w     15.00  94.00   0.50    0.05    --   46.63-125.00  90.00  158
 23  \w     48.00  74.00   0.50    0.05    --  104.75-125.00 -60.00   52
 24  \w     32.00  57.00   0.50    0.05    --  104.75 -94.00 -60.00   50
 25  \w     78.00 107.00   0.50    0.05    --  104.75 -94.00 -30.00   58
 26  \w     90.00 117.00   0.50    0.05    --  104.75-125.00 -60.00   54
 27  \w     35.00 117.00   0.50    0.05    --  104.75-125.00-180.00  164
 28  \w     36.00 103.00   0.50    0.05    --  104.75 -94.00-120.00  134
 29  \w     68.00  97.00   0.50    0.05    --  104.75 -94.00 -60.00   58
 30  \w     32.00  64.00   0.50    0.05    --  104.75 -94.00 -30.00   64
 31  \w    -28.00  27.00   0.50    0.05    --   46.63 -17.00 -36.00  110
 32  \w    -25.00  62.00   0.50    0.05    --   46.63 -57.00 -60.00  174
 33  \w    -13.00  16.00   0.50    0.05    --   22.00 102.00-102.45   58
 34  \w     13.00  45.00   0.50    0.05    --   42.00  90.00-102.63   64
 35  \w    -43.00 -12.00   0.50    0.05    --    6.00 127.00-120.25   62
 36  \w     29.00 126.00   0.50    0.05    --   54.00  83.00 140.59  194
 37  \w      3.00  33.00   0.50    0.05    --   34.00  95.00 145.30   60
 38  \w    -13.00  16.00   0.50    0.05    --   22.00 102.00 121.66   58
 39  \w     14.00  45.00   0.50    0.05    --   42.00  89.00 107.14   62
 40  \w     17.00  45.00   0.50    0.05    --   46.00  90.00  45.69   56
 41  \w     17.00  45.00   0.50    0.05    --   46.00  90.00 -54.91   56
 42  \w     25.00 122.00   0.50    0.05    --   50.00  83.00-174.02  194
 43  \w   -139.00 -40.00   0.50    0.05    --  -66.00 -83.00-179.70  198
 44  \w   -158.00-111.00   0.50    0.05    --  -86.00 -83.00-118.20   94
 45  \w    -88.00 -60.00   0.50    0.05    --  -86.00 -83.00-118.20   56
 46  \w   -146.00 -48.00   0.50    0.05    --  -74.00 -83.00-102.71  196
 47  \w   -143.00 -45.00   0.50    0.05    --  -70.00 -82.00-100.96  196
 48  \w   -135.00 -37.00   0.50    0.05    --  -62.00 -82.00-139.89  196
 49  \w    -80.00 -54.00   0.50    0.05    --  -78.00 -83.00  26.07   52
 50  \w   -143.00 -44.00   0.50    0.05    --  -70.00 -83.00  77.02  198
 51  \w   -150.00-124.00   0.50    0.05    --  -78.00 -82.00 165.13   52
 52  \w    -83.00 -53.00   0.50    0.05    --  -78.00 -82.00 165.13   60
 53  \w   -121.00 -33.00   0.50    0.05    --  -46.63 -17.00 -36.00  176
 54  \w   -102.00 -76.00   0.50    0.05    --  -98.00 -78.00 124.74   52
 55  \w   -154.00-128.00   0.50    0.05    --  -98.00 -78.00 124.74   52
 56  \w   -169.00-115.00   0.50    0.05    --  -98.00 -76.00 -76.82  108
 57  \w   -163.00-111.00   0.50    0.05    --  -94.00 -76.00 -68.25  104
 58  \w   -106.00 -78.00   0.50    0.05    --  -98.00 -76.00 -76.82   56
 59  \w   -146.00 -51.00   0.50    0.05    --  -74.00 -78.00-176.42  190
 60  \w   -143.00 -77.00   0.50    0.05    --  -98.00 -77.00 -93.49  132
 61  \w   -107.00 -72.00   0.50    0.05    --  -94.00 -76.00 -68.25   70
 62  \w    -94.00 -64.00   0.50    0.05    --  -86.00 -75.00 -66.39   60
 63  \w   -107.00 -70.00   0.50    0.05    --  -90.00 -74.00  -7.48   74
 64  \w   -108.00 -74.00   0.50    0.05    --  -94.00 -74.00  35.89   68
 65  \w   -165.00-117.00   0.50    0.05    --  -94.00 -74.00  35.89   96
 66  \w   -146.00 -52.00   0.50    0.05    --  -74.00 -75.00 135.77  188
 67  \w   -115.00 -79.00   0.50    0.05    -- -102.00 -76.00 170.73   72
 68  \w   -173.00-123.00   0.50    0.05    -- -102.00 -76.00 170.73  100
 69  \w   -146.00 -52.00   0.50    0.05    --  -74.00 -74.00 106.19  188
 70  \w    -93.00 -68.00   0.50    0.05    --  -90.00 -74.00  57.53   50
 71  \w   -156.00-113.00   0.50    0.05    --  -90.00 -74.00  57.53   86
 72  \w   -161.00-131.00   0.50    0.05    --  -90.00 -74.00  49.24   60
 73  \w   -162.00-122.00   0.50    0.05    --  -90.00 -74.00  -7.48   80
 74  \w   -135.00 -40.00   0.50    0.05    --  -62.00 -74.00 -90.21  190
 75  \w   -146.00 -52.00   0.50    0.05    --  -74.00 -74.00 -17.28  188
 76  \w   -152.00 -69.00   0.50    0.05    --  -90.00 -74.00  17.02  166
 77  \w    -88.00 -62.00   0.50    0.05    --  -82.00 -73.00 -42.94   52
 78  \w   -143.00 -49.00   0.50    0.05    --  -70.00 -73.00 -41.19  188
 79  \w    -95.00 -70.00   0.50    0.05    --  -90.00 -74.00  49.24   50
 80  \w    -86.00 -61.00   0.50    0.05    --  -82.00 -73.00 101.23   50
 81  \w    -92.00 -60.00   0.50    0.05    --  -78.00 -73.00  78.12   64
 82  \w    -94.00 -69.00   0.50    0.05    --  -90.00 -72.00 136.79   50
 83  \w    -88.00 -62.00   0.50    0.05    --  -82.00 -73.00  57.27   52
 84  \w   -138.00 -81.00   0.50    0.05    -- -102.00 -72.00  77.59  114
 85  \w   -162.00-109.00   0.50    0.05    --  -90.00 -72.00 136.79  106
 86  \w   -101.00 -65.00   0.50    0.05    --  -86.00 -72.00 170.40   72
 87  \w    -84.00 -58.00   0.50    0.05    --  -78.00 -73.00  33.10   52
 88  \w    -99.00 -62.00   0.50    0.05    --  -82.00 -73.00   0.56   74
 89  \w   -175.00-142.00   0.50    0.05    -- -102.00 -72.00  77.59   66
 90  \w   -162.00 -70.00   0.50    0.05    --  -90.00 -71.00 -24.91  184
 91  \w    -92.00 -65.00   0.50    0.05    --  -86.00 -72.00 -57.35   54
 92  \w   -142.00 -78.00   0.50    0.05    --  -98.00 -69.00-164.00  128
 93  \w   -163.00 -74.00   0.50    0.05    --  -94.00 -71.00-154.74  178
 94  \w   -146.00 -54.00   0.50    0.05    --  -74.00 -69.00-155.52  184
 95  \w    -91.00 -65.00   0.50    0.05    --  -82.00 -72.00-104.32   52
 96  \w   -147.00-121.00   0.50    0.05    --  -90.00 -64.00-137.26   52
 97  \w   -159.00-106.00   0.50    0.05    --  -86.00 -68.00  65.56  106
 98  \w    -92.00 -67.00   0.50    0.05    --  -86.00 -68.00  65.56   50
 99  \w   -101.00 -76.00   0.50    0.05    --  -94.00 -65.00  87.32   50
100  \w   -165.00-107.00   0.50    0.05    --  -94.00 -65.00  87.32  116
101  \w   -152.00 -86.00   0.50    0.05    -- -102.00 -62.00 117.08  132
102  \w   -160.00 -75.00   0.50    0.05    --  -90.00 -63.00 -48.13  170
103  \w   -106.00 -80.00   0.50    0.05    --  -90.00 -64.00-137.26   52
104  \w   -153.00-111.00   0.50    0.05    --  -90.00 -58.00-123.18   84
105  \w   -175.00 -89.00   0.50    0.05    -- -102.00 -17.00 -36.00  172
106  \w   -102.00 -60.00   0.50    0.05    -- -102.00  77.00 150.00   84
107  \w    -68.00 -34.00   0.50    0.05    -- -102.00  61.00 120.00   68
108  \w    -23.00  29.00   0.50    0.05    --  -46.63  17.00 131.00  104
109  \w    -66.00 -40.00   0.50    0.05    -- -102.00  61.00-150.00   52
110  \w   -116.00 -32.00   0.50    0.05    -- -102.00 125.00-150.00  168
111  \w    -69.00 -33.00   0.50    0.05    -- -102.00 125.00   0.00   72
112  \w   -112.00 -82.00   0.50    0.05    -- -102.00 125.00   0.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0525998000
_diffrn_orient_matrix_UB_12      0.1333223000
_diffrn_orient_matrix_UB_13      0.0169793000
_diffrn_orient_matrix_UB_21      0.1312148000
_diffrn_orient_matrix_UB_22      -0.0090030000
_diffrn_orient_matrix_UB_23      0.0179232000
_diffrn_orient_matrix_UB_31      0.0481646000
_diffrn_orient_matrix_UB_32      0.0494654000
_diffrn_orient_matrix_UB_33      -0.1007561000
_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  0.0542
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            79604
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.430
_diffrn_reflns_theta_min         4.089
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.985
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21046
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.432
_exptl_crystal_description       plate
_exptl_crystal_F_000             820
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.259
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     494
_refine_ls_number_reflns         7356
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0325
_refine_ls_R_factor_gt           0.0313
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0386P)^2^+1.3658P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0808
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7041
_reflns_number_total             7356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06436k2.cif
_cod_data_source_block           exp_13456_auto
_cod_database_code               1571358
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONCl
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.980
_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.a Secondary CH2 refined with riding coordinates:
 C00X(H00A,H00B), C017(H01D,H01E)
2.b Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00P(H00P), C00S(H00S), C00V(H00V), C00Z(H00Z), C011(H011),
 C012(H012), C013(H013), C014(H014), C016(H016), C018(H018), C01A(H01I),
 C01B(H01J), C01C(H01K), C01F(H01R)
2.c Idealised Me refined as rotating group:
 C015(H01A,H01B,H01C), C019(H01F,H01G,H01H), C01D(H01L,H01M,H01N), C01E(H01O,
 H01P,H01Q), C01G(H01S,H01T,H01U), C01H(H01V,H01W,H01X), C01I(H01Y,H,HA)
;
_shelx_res_checksum              38847
_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 7.169
_oxdiff_exptl_absorpt_empirical_full_min 0.711