<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_1571359
_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         'C34 H37 N9 O4'
_chemical_formula_sum            'C34 H37 N9 O4'
_chemical_formula_weight         635.72
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-08-01
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-10-27 deposited with the CCDC.	2024-01-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.6160(7)
_cell_length_b                   13.0934(5)
_cell_length_c                   9.9979(3)
_cell_measurement_reflns_used    19984
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      76.6230
_cell_measurement_theta_min      3.3260
_cell_volume                     3222.39(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_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 0.988
_diffrn_measured_fraction_theta_max 0.964
_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   -118.00 -24.00   0.50    0.05    --  -46.63 -77.00  90.00  188
  2  \w   -118.00 -47.00   0.50    0.05    --  -46.63 -77.00 -30.00  142
  3  \w   -118.00 -32.00   0.50    0.05    --  -46.63 -57.00-180.00  172
  4  \w    -40.00  27.00   0.50    0.05    --  -46.63  37.00-150.00  134
  5  \w    -69.00 -29.00   0.50    0.05    -- -102.00  61.00 150.00   80
  6  \w    -69.00 -29.00   0.50    0.05    -- -102.00  61.00  60.00   80
  7  \w    -69.00 -29.00   0.50    0.05    -- -102.00  61.00 -30.00   80
  8  \w     82.00 178.00   0.50    0.05    --  104.75  77.00   0.00  192
  9  \w     91.00 178.00   0.50    0.05    --  104.75  15.00 -77.00  174
 10  \w     32.00  73.00   0.50    0.05    --  104.75 -61.00  30.00   82
 11  \w     32.00  73.00   0.50    0.05    --  104.75 -61.00   0.00   82
 12  \w     92.00 177.00   0.50    0.05    --  104.75  45.00-150.00  170
 13  \w     32.00  73.00   0.50    0.05    --  104.75 -61.00-180.00   82
 14  \w    -28.00  28.00   0.50    0.05    --   46.63 -19.00   0.00  112
 15  \w     32.00  73.00   0.50    0.05    --  104.75 -61.00  90.00   82
 16  \w     32.00 109.00   0.50    0.05    --  104.75 -94.00  30.00  154
 17  \w      7.00  85.00   0.50    0.05    --   46.63-113.00 -52.00  156
 18  \w     32.00 132.00   0.50    0.05    --  104.75-147.00-120.00  200
 19  \w     36.00 112.00   0.50    0.05    --  104.75-113.00 -52.00  152
 20  \w     35.00 117.00   0.50    0.05    --  104.75-125.00   0.00  164
;
_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      -0.0109198000
_diffrn_orient_matrix_UB_12      0.1151992000
_diffrn_orient_matrix_UB_13      -0.0163860000
_diffrn_orient_matrix_UB_21      -0.0042007000
_diffrn_orient_matrix_UB_22      -0.0139763000
_diffrn_orient_matrix_UB_23      -0.1526239000
_diffrn_orient_matrix_UB_31      -0.0614504000
_diffrn_orient_matrix_UB_32      -0.0197450000
_diffrn_orient_matrix_UB_33      0.0134040000
_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  0.0522
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            27752
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.093
_diffrn_reflns_theta_min         3.591
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.727
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43493
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       needle
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.181
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 2417 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     472
_refine_ls_number_reflns         6548
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0420
_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^)+(0.0541P)^2^+0.9332P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1057
_refine_ls_wR_factor_ref         0.1140
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                6031
_reflns_number_total             6548
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06436k2.cif
_cod_data_source_block           exp_16702_auto
_cod_database_code               1571359
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONCl
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.899
_olex2_refinement_description
;
1. Restrained distances
 C00Q-C015 \\sim C00Q-C0
 with sigma of 0.02
 C015-C019 \\sim C0-C3
 with sigma of 0.02
 C015-C1 \\sim C0-C1A
 with sigma of 0.02
 C015-C2 \\sim C0-C2A
 with sigma of 0.02
 C00Q-C019 \\sim C00Q-C3
 with sigma of 0.04
 C00Q-C1 \\sim C00Q-C1A
 with sigma of 0.04
 C00Q-C2 \\sim C00Q-C2A
 with sigma of 0.04
 C019-C1 \\sim C3-C1A
 with sigma of 0.04
 C019-C2 \\sim C3-C2A
 with sigma of 0.04
 C1-C2 \\sim C1A-C2A
 with sigma of 0.04
2. Others
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C0)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(H3C)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(C015)=Sof(C019)=Sof(H01J)=Sof(H01K)=Sof(H01L)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C00X(H00G,H00H)
3.b Aromatic/amide H refined with riding coordinates:
 C00O(H00O), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U), C00Y(H00Y),
 C00Z(H00Z), C011(H011), C013(H013), C014(H014), C017(H017)
3.c Idealised Me refined as rotating group:
 C00V(H00A,H00B,H00C), C00W(H00D,H00E,H00F), C012(H01A,H01B,H01C), C016(H01D,
 H01E,H01F), C018(H01G,H01H,H01I), C019(H01J,H01K,H01L), C1(H1A,H1B,H1C),
 C2(H2A,H2B,H2C), C2A(H2AA,H2AB,H2AC), C3(H3A,H3B,H3C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              69032
_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 2.634
_oxdiff_exptl_absorpt_empirical_full_min 0.571