Asymmetric Synthesis of Planar-chiral Metacyclophanes via Aromatic Amination enabled Enantioselective Desymmetrization
Zhou, Changyu; Zhou, Jinmiao; Zhang, Lele; Xie, Wansen; Gu, Huanchao; Liu, Hua; Yang, Xiaoyu; Chemical Science  (2026) –; doi:10.1039/D5SC09849A

data_1576529
_publ_section_title
;
 Asymmetric synthesis of planar-chiral metacyclophanes <i>via</i> aromatic
 amination enabled enantioselective desymmetrization.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              7582
_journal_page_last               7589
_journal_paper_doi               10.1039/d5sc09849a
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H39 Br N4 O4'
_chemical_formula_sum            'C32 H39 Br N4 O4'
_chemical_formula_weight         623.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-11-06 deposited with the CCDC.	2026-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.6989(6)
_cell_length_b                   19.377(2)
_cell_length_c                   28.148(3)
_cell_measurement_reflns_used    2253
_cell_measurement_temperature    230.0
_cell_measurement_theta_max      35.11
_cell_measurement_theta_min      2.41
_cell_volume                     3108.3(6)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      230.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.1007
_diffrn_reflns_av_unetI/netI     0.1910
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            13476
_diffrn_reflns_point_group_measured_fraction_full 0.958
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         53.893
_diffrn_reflns_theta_min         2.408
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           3.57
_diffrn_source_power             0.2494716
_diffrn_source_target            Mo
_diffrn_source_voltage           69.88
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.403
_exptl_absorpt_correction_T_max  0.4581
_exptl_absorpt_correction_T_min  0.3378
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1033 before and 0.0732 after correction.
The Ratio of minimum to maximum transmission is 0.7374.
The \l/2 correction factor is Not present.
;
_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    1.333
_exptl_crystal_description       block
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.796
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 682 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(4)
_refine_ls_extinction_coef       0.0115(12)
_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   0.967
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         5436
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      0.967
_refine_ls_R_factor_all          0.1673
_refine_ls_R_factor_gt           0.0788
_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^)+(0.0786P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1815
_refine_ls_wR_factor_ref         0.2331
_reflns_Friedel_coverage         0.698
_reflns_Friedel_fraction_full    0.936
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                2654
_reflns_number_total             5436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09849a2.cif
_cod_data_source_block           ghc_zcy_4_27_0m
_cod_depositor_comments
'Adding full bibliography for 1576529--1576530.cif.'
_cod_original_cell_volume        3108.2(6)
_cod_database_code               1576529
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.872
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C00F-C00D
 1.396 with sigma of 0.00001
 C00G-C00C
 1.414 with sigma of 0.00001
 C00G-C00D
 1.328 with sigma of 0.00001
 C00F-C00A
 1.409 with sigma of 0.00001
 C00E-C00C
 1.376 with sigma of 0.00001
 C00E-C00A
 1.394 with sigma of 0.00001
3.a Riding coordinates:
 N00B(H00B)
3.b Secondary CH2 refined with riding coordinates:
 C00K(H00A,H00C), C00L(H00E,H00F), C00O(H00G,H00H), C00P(H00I,H00J), C00S(H00K,
 H00L), C00W(H00P,H00Q), C00Y(H00U,H00V), C00Z(H00W,H00Y), C010(H01A,H01B),
 C012(H01C,H01D), C015(H01E,H01F)
3.c Aromatic/amide H refined with riding coordinates:
 N007(H007), C00D(H00D), C00X(H00X), C011(H011), C00Q(H00R), C00M(H00S),
 C00N(H00T), C014(H014), C00R(H00Z), C00V(H00), C00T(H1), C013(H013)
3.d Fitted hexagon refined as free rotating group:
 C00X(C011,C00Q,C00M,C00N,C00I), C014(C00R,C00V,C00J,C00T,C013)
3.e Idealised Me refined as rotating group:
 C00U(H00M,H00N,H00O)
;
_shelx_res_checksum              46992
_olex2_submission_special_instructions 'No special instructions were received'