Carbene-organocatalyzed enantioselective [5+5] annulation of dienols and dienals towards tetrahydroisochromen-1-ones.
Xu, Ke; Zhao, Jiayi; Lin, Kejun; Zhu, Tingshun; Chemical communications (Cambridge, England) 61 (2025) 10602–10605; doi:10.1039/d5cc02347e

data_7134664
_publ_section_title
;
 Carbene-organocatalyzed enantioselective [5+5] annulation of dienols and
 dienals towards tetrahydroisochromen-1-ones.
;
_journal_issue                   57
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10602
_journal_page_last               10605
_journal_paper_doi               10.1039/d5cc02347e
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C H2 Cl2, C31 H27 N O6'
_chemical_formula_sum            'C32 H29 Cl2 N O6'
_chemical_formula_weight         594.46
_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             2023-02-25
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-02-25 deposited with the CCDC.	2025-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.5740(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.02860(10)
_cell_length_b                   19.9167(2)
_cell_length_c                   10.57480(10)
_cell_measurement_reflns_used    8381
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.0170
_cell_measurement_theta_min      4.4260
_cell_volume                     1438.98(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Pilatus3R 200K-A'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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    -46.00  25.00   0.50    1.00    --    0.00 -77.00 150.00  142
  2  \w    -46.00  19.00   0.50    1.00    --    0.00 -77.00 -90.00  130
  3  \w    -13.00  18.00   0.50    1.00    --    0.00 -82.00 120.00   62
  4  \w     36.00  61.00   0.50    1.00    --    0.00  57.00  60.00   50
  5  \w    125.00 152.00   0.50    3.00    --   64.00  75.00-144.40   54
  6  \w     37.00  83.00   0.50    3.00    --   64.00  75.00-144.40   92
  7  \w     87.00 120.00   0.50    3.00    --   64.00  75.00-144.40   66
  8  \w     48.00 126.00   0.50    3.00    --   95.80 -82.00   0.00  156
  9  \w     90.00 126.00   0.50    3.00    --   95.80 -82.00-150.00   72
 10  \w      7.00  44.00   0.50    3.00    --   95.80 -82.00   0.00   74
 11  \w     98.00 135.00   0.50    3.00    --   95.80  82.00  60.00   74
 12  \w      7.00 119.00   0.50    3.00    --   95.80 -61.00   0.00  224
 13  \w     72.00 185.00   0.50    3.00    --   95.80  15.00 -30.00  226
 14  \w     42.00 111.00   0.50    3.00    --   95.80 -82.00 150.00  138
 15  \w     51.00  81.00   0.50    3.00    --   95.80 -82.00-150.00   60
 16  \w     72.00  99.00   0.50    3.00    --   95.80 -30.00  30.00   54
 17  \w     87.00 184.00   0.50    3.00    --   95.80  82.00 -60.00  194
 18  \w     80.00 105.00   0.50    3.00    --   95.80 -82.00  60.00   50
 19  \w     59.00 122.00   0.50    3.00    --   95.80 -82.00 -90.00  126
 20  \w      7.00  47.00   0.50    3.00    --   95.80 -15.00  90.00   80
 21  \w     66.00 119.00   0.50    3.00    --   95.80 -15.00  90.00  106
 22  \w      7.00  66.00   0.50    3.00    --   95.80 -30.00 -90.00  118
 23  \w      9.00  62.00   0.50    3.00    --   95.80 -30.00  30.00  106
 24  \w      6.00  40.00   0.50    3.00    --   95.80 -82.00 -90.00   68
 25  \w     17.00 109.00   0.50    3.00    --   95.80 -45.00-180.00  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0122261000
_diffrn_orient_matrix_UB_12      -0.0755085000
_diffrn_orient_matrix_UB_13      0.0323210000
_diffrn_orient_matrix_UB_21      -0.2249587000
_diffrn_orient_matrix_UB_22      -0.0045964000
_diffrn_orient_matrix_UB_23      -0.0381784000
_diffrn_orient_matrix_UB_31      0.0074615000
_diffrn_orient_matrix_UB_32      -0.0160762000
_diffrn_orient_matrix_UB_33      -0.1413440000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            15310
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.278
_diffrn_reflns_theta_min         4.301
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'MicroMax 007 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.415
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96401
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.372
_exptl_crystal_description       block
_exptl_crystal_F_000             620
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.388
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2295 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.023(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     373
_refine_ls_number_reflns         5652
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0501P)^2^+0.2131P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0926
_refine_ls_wR_factor_ref         0.0944
_reflns_Friedel_coverage         0.897
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                5304
_reflns_number_total             5652
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02347e2.cif
_cod_data_source_block           fck11pc7_collect
_cod_depositor_comments
'Adding full bibliography for 7134660--7134669.cif.'
_cod_database_code               7134664
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C64 H58 Cl4 N2 O12 '
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.794
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C6(H6), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C23(H23), C26(H26), C19(H19), C15(H15), C18(H18), C32(H32), C16(H16),
 C33(H33), C35(H35), C34(H34), C25(H25), C36(H36), C24(H24)
2.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              6941
_shelx_hkl_checksum              2766
_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 1.288
_oxdiff_exptl_absorpt_empirical_full_min 0.712