Cationic iridium-catalyzed enantioselective decarboxylative aryl addition of aromatic carboxylic acids to bicyclic alkenes.
Asano, Ren; Nonami, Reina; Hamasaki, Hina; Kanemoto, Kazuya; Fujita, Harunori; Yamamoto, Kaisei; Seki, Tomohiro; Shibatomi, Kazutaka; Kuwahara, Shunsuke; Shirai, Tomohiko; Chemical communications (Cambridge, England) 62 (2026) 6096–6100; doi:10.1039/d6cc00389c

data_7135370
_publ_section_title
;
 Cationic iridium-catalyzed enantioselective decarboxylative aryl addition
 of aromatic carboxylic acids to bicyclic alkenes.
;
_journal_issue                   22
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6096
_journal_page_last               6100
_journal_paper_doi               10.1039/d6cc00389c
_journal_volume                  62
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C H2 Cl2, C17 H23 N O'
_chemical_formula_sum            'C18 H25 Cl2 N O'
_chemical_formula_weight         342.29
_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             2025-12-11
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-12-11 deposited with the CCDC.	2026-02-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.961(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1647(3)
_cell_length_b                   9.6045(2)
_cell_length_c                   15.8224(4)
_cell_measurement_reflns_used    10427
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      76.2060
_cell_measurement_theta_min      3.0050
_cell_volume                     1828.18(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.990
_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     95.00 178.00   0.50    0.32    --  107.14  19.00 150.00  166
  2  \w     25.00 119.00   0.50    0.08    --   47.43  77.00 150.00  188
  3  \w     25.00 119.00   0.50    0.08    --   47.43  77.00  90.00  188
  4  \w     35.00 120.00   0.50    0.08    --   47.43  38.00  60.00  170
  5  \w     33.00  66.00   0.50    0.08    --   47.43  57.00-120.00   66
  6  \w     35.00  69.00   0.50    0.32    --  107.14 -57.00-120.00   68
  7  \w     35.00  69.00   0.50    0.32    --  107.14 -57.00 -90.00   68
  8  \w     35.00  69.00   0.50    0.32    --  107.14 -57.00  30.00   68
  9  \w     35.00  69.00   0.50    0.32    --  107.14 -57.00  60.00   68
 10  \w     12.00  87.00   0.50    0.08    --   47.43-115.00  55.00  150
 11  \w     37.00 106.00   0.50    0.32    --  107.14 -99.00 -90.00  138
 12  \w     39.00 109.00   0.50    0.32    --  107.14-115.00  55.00  140
 13  \w     39.00 108.00   0.50    0.32    --  107.14-111.00 145.00  138
 14  \w    -27.00  30.00   0.50    0.08    --   47.43 -19.00 120.00  114
 15  \w   -119.00 -25.00   0.50    0.08    --  -47.43 -77.00 -60.00  188
 16  \w    -27.00  31.00   0.50    0.08    --   47.43 -20.00-111.00  116
 17  \w     49.00 119.00   0.50    0.08    --   47.43 175.00 -75.00  140
 18  \w    -40.00  26.00   0.50    0.08    --  -47.43  38.00-180.00  132
 19  \w    -62.00 -32.00   0.50    0.32    -- -104.50  57.00-120.00   60
 20  \w   -174.00 -92.00   0.50    0.32    -- -104.50 -19.00 -30.00  164
 21  \w   -174.00 -91.00   0.50    0.32    -- -104.50 -20.00-111.00  166
 22  \w   -174.00 -92.00   0.50    0.32    -- -104.50 -19.00-150.00  164
 23  \w   -174.00 -82.00   0.50    0.32    -- -104.50 -77.00  60.00  184
 24  \w   -174.00 -91.00   0.50    0.32    -- -104.50 -38.00  90.00  166
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1024322000
_diffrn_orient_matrix_UB_12      0.0364696000
_diffrn_orient_matrix_UB_13      0.0195071000
_diffrn_orient_matrix_UB_21      -0.0756042000
_diffrn_orient_matrix_UB_22      -0.0201116000
_diffrn_orient_matrix_UB_23      -0.1031930000
_diffrn_orient_matrix_UB_31      -0.0142724000
_diffrn_orient_matrix_UB_32      -0.1548253000
_diffrn_orient_matrix_UB_33      0.0180481000
_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  0.0758
_diffrn_reflns_av_unetI/netI     0.0695
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18745
_diffrn_reflns_point_group_measured_fraction_full 0.891
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.202
_diffrn_reflns_theta_min         3.056
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.193
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48899
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1879 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     403
_refine_ls_number_reflns         5954
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0539P)^2^+0.0179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1098
_refine_ls_wR_factor_ref         0.1151
_reflns_Friedel_coverage         0.688
_reflns_Friedel_fraction_full    0.778
_reflns_Friedel_fraction_max     0.775
_reflns_number_gt                5257
_reflns_number_total             5954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00389c2.cif
_cod_data_source_block           req-001_autored
_cod_depositor_comments          'Adding full bibliography for 7135370.cif.'
_cod_database_code               7135370
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         CHNO
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.362
_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.a Ternary CH refined with riding coordinates:
 C00H(H00H), C00J(H00O), C00L(H00L), C00S(H00W), C00U(H00X), C017(H017)
2.b Secondary CH2 refined with riding coordinates:
 C00R(H00U,H00V), C00W(H00Y,H), C00X(H00G,H00I), C00Y(H00Z,HA), C00Z(H00J,
 H00K), C010(H01H,H01I), C012(H01D,H01E), C015(H01R,H01S), C016(H01P,H01Q),
 C018(H01F,H01G)
2.c Aromatic/amide H refined with riding coordinates:
 N007(H007), N008(H008), C00E(H00M), C00N(H00N), C00P(H00T), C00Q(H00Q)
2.d Idealised Me refined as rotating group:
 C00I(H00A,H00B,H00C), C00K(H00P,H00R,H00S), C00V(H00D,H00E,H00F), C011(H01A,
 H01B,H01C), C013(H01J,H01K,H01L), C014(H01M,H01N,H01O)
;
_shelx_res_checksum              3689
_shelx_hkl_checksum              33493
_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 3.966
_oxdiff_exptl_absorpt_empirical_full_min 0.289