<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_1571360
_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 O5, 4(C0.125 Cl0.25)'
_chemical_formula_sum            'C34.5 H38 Cl N9 O5'
_chemical_formula_weight         694.19
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-10-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-26 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            8
_cell_length_a                   14.2497(2)
_cell_length_b                   36.7753(5)
_cell_length_c                   14.4950(2)
_cell_measurement_reflns_used    6052
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      62.500
_cell_measurement_theta_min      3.326
_cell_volume                     7595.92(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (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, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            34722
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        62.500
_diffrn_reflns_theta_max         62.500
_diffrn_reflns_theta_min         3.326
_exptl_absorpt_coefficient_mu    1.311
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84938
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.214
_exptl_crystal_description       needle
_exptl_crystal_F_000             2920
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.021
_refine_diff_density_min         -0.793
_refine_diff_density_rms         0.109
_refine_ls_extinction_coef       0.00052(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.202
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         6052
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      1.246
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0857
_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^)+(0.1464P)^2^+10.8090P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2538
_refine_ls_wR_factor_ref         0.2575
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5582
_reflns_number_total             6052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06436k2.cif
_cod_data_source_block           A_CCDC1
_cod_original_formula_sum        'C34.50 H38 Cl N9 O5'
_cod_database_code               1571360
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Shared sites
{C35, C35A}
2. Restrained distances
 C35-Cl1 = C35A-Cl1A
 1.76 with sigma of 0.01
 C36-Cl2 = C36-Cl3
 1.76 with sigma of 0.01
 Cl2-Cl3
 2.85 with sigma of 0.02
 C37-Cl4 = C37-Cl5
 1.76 with sigma of 0.01
 Cl4-Cl5
 2.85 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(Cl1)
\\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl4) \\sim Ueq,
Uanis(Cl5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl1) \\sim Ueq, Uanis(Cl1A) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C35A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35) = Uanis(C35A)
Uanis(C36) = Uanis(Cl2) = Uanis(Cl3)
Uanis(Cl4) = Uanis(Cl5) = Uanis(C37)
Uanis(C35) = Uanis(C35A) = Uanis(Cl1) = Uanis(Cl1A)
4. Others
 Fixed Sof: C35(0.125) C35A(0.125) C36(0.125) C37(0.125) Cl1(0.25) Cl1A(0.25)
 Cl2(0.125) Cl3(0.125) Cl4(0.125) Cl5(0.125)
5.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B)
5.b Me refined with riding coordinates:
 C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3A), C5(H5A), C11(H11A), C13(H13A), C14(H14A), C27(H27A), C28(H28A),
 C29(H29A), C30(H30A), C31(H31A), N5(H5B)
;
_shelx_res_checksum              67279
_olex2_submission_special_instructions 'No special instructions were received'