Pd-catalyzed asymmetric etherification of 2<i>H</i>-chromenes: enantioselective construction of chiral 4-alkoxy-4<i>H</i>-chromenes.
Wang, Bangzhong; Sun, Luyang; Zhang, Pengyue; Zhang, Shuaibo; Zhao, Jinfeng; Qu, Jingping; Zhou, Yuhan; Organic & biomolecular chemistry 23 (2025) 3431–3436; doi:10.1039/d5ob00005j

data_7160402
_publ_section_title
;
 Pd-catalyzed asymmetric etherification of 2<i>H</i>-chromenes:
 enantioselective construction of chiral 4-alkoxy-4<i>H</i>-chromenes.
;
_journal_issue                   14
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3431
_journal_page_last               3436
_journal_paper_doi               10.1039/d5ob00005j
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C24 H23 Br F3 N O8'
_chemical_formula_sum            'C24 H23 Br F3 N O8'
_chemical_formula_weight         590.34
_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             2024-12-31
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-31 deposited with the CCDC.	2025-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.168(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.7404(11)
_cell_length_b                   8.3449(8)
_cell_length_c                   13.0752(12)
_cell_measurement_reflns_used    5377
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      19.82
_cell_measurement_theta_min      2.25
_cell_volume                     1277.6(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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_temperature      120.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1086
_diffrn_reflns_av_unetI/netI     0.0859
_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       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            30400
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.022
_diffrn_reflns_theta_max         25.022
_diffrn_reflns_theta_min         1.739
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.679
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5078
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1462 before and 0.0975 after correction.
The Ratio of minimum to maximum transmission is 0.6813.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.535
_exptl_crystal_description       needle
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.627
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 1261 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     365
_refine_ls_number_reflns         4505
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0788
_refine_ls_R_factor_gt           0.0536
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0635P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1208
_refine_ls_wR_factor_ref         0.1336
_reflns_Friedel_coverage         0.860
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3504
_reflns_number_total             4505
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00005j2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7160402.cif.'
_cod_database_code               7160402
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.633
_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
 N009-O00C \\sim N0-O00D
 with sigma of 0.02
 N009-O00F \\sim N0-O00G
 with sigma of 0.02
 N009-C00Y \\sim N0-C00Y
 with sigma of 0.02
 O00C-O00F \\sim O00D-O00G
 with sigma of 0.04
 O00C-C00Y \\sim O00D-C00Y
 with sigma of 0.04
 O00F-C00Y \\sim O00G-C00Y
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N009 \\sim O00F \\sim O00G \\sim O00C \\sim N0 \\sim O00D: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C00Y, N009, O00F, O00C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O00G, N0, C00Y, O00D
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(N0)=Sof(O00G)=Sof(O00D)=1-FVAR(1)
 Sof(N009)=Sof(O00C)=Sof(O00F)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C00E(H00E), C00U(H00U)
6.b Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00K(H00C,H00D), C00Q(H00F,H00G)
6.c Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00M(H00M), C00P(H00P), C00R(H00R), C00S(H00S), C00V(H00V)
6.d Idealised Me refined as rotating group:
 C00Z(H00H,H00J,H00K), C010(H01A,H01B,H01C), C011(H01D,H01E,H01F)
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_shelx_res_checksum              23298
_olex2_submission_special_instructions 'No special instructions were received'