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_7134665
_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, C32 H27 N O4'
_chemical_formula_sum            'C33 H29 Cl2 N O4'
_chemical_formula_weight         574.47
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 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                90.9030(10)
_cell_angle_beta                 104.2710(10)
_cell_angle_gamma                97.5320(10)
_cell_formula_units_Z            1
_cell_length_a                   7.28960(10)
_cell_length_b                   9.99900(10)
_cell_length_c                   10.3560(2)
_cell_measurement_reflns_used    15884
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.0390
_cell_measurement_theta_min      4.4080
_cell_volume                     724.321(19)
_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 0.996
_diffrn_measured_fraction_theta_max 0.973
_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    -33.00  31.00   0.50    0.50    --    0.00 -82.00  60.00  128
  2  \w    -57.00  52.00   0.50    0.50    --   32.00 -50.00-108.81  218
  3  \w      9.00 125.00   0.50    0.50    --   36.00  72.00-150.70  232
  4  \w     13.00 129.00   0.50    0.50    --   40.00  72.00 -19.05  232
  5  \w     25.00 141.00   0.50    0.70    --   52.00  72.00  92.71  232
  6  \w     31.00 145.00   0.50    0.70    --   56.00  74.00-174.43  228
  7  \w     33.00 149.00   0.50    0.70    --   60.00  72.00  32.91  232
  8  \w     32.00 149.00   0.50    0.70    --   60.00  74.00-101.94  234
  9  \w     33.00 149.00   0.50    0.70    --   60.00  73.00 -29.89  232
 10  \w     37.00 153.00   0.50    0.70    --   64.00  73.00  92.21  232
 11  \w     41.00 157.00   0.50    0.70    --   68.00  73.00-155.42  232
 12  \w     44.00 161.00   0.50    0.70    --   72.00  74.00 -64.75  234
 13  \w     44.00 161.00   0.50    0.70    --   72.00  74.00 126.75  234
 14  \w     45.00 161.00   0.50    0.70    --   72.00  71.00  -8.81  232
 15  \w     46.00 161.00   0.50    0.70    --   72.00  69.00  49.71  230
 16  \w     48.00 165.00   0.50    0.70    --   76.00  75.00-141.20  234
 17  \w     51.00 165.00   0.50    0.70    --   76.00  67.00  94.78  228
 18  \w     72.00 185.00   0.50    0.70    --   95.80  61.00-120.00  226
 19  \w      6.00 125.00   0.50    0.70    --   95.80 -77.00 150.00  238
 20  \w     72.00 185.00   0.50    0.70    --   95.80  61.00 -30.00  226
 21  \w     74.00  99.00   0.50    0.70    --   95.80  61.00  30.00   50
 22  \w     79.00 104.00   0.50    0.70    --   95.80 -82.00 -60.00   50
 23  \w     74.00 182.00   0.50    0.70    --   95.80  61.00   0.00  216
 24  \w      6.00 120.00   0.50    0.70    --   95.80 -82.00  30.00  228
 25  \w     49.00  95.00   0.50    0.70    --   95.80 -61.00-150.00   92
 26  \w    119.00 161.00   0.50    0.70    --   95.80  62.00-132.22   84
 27  \w      8.00  45.00   0.50    0.70    --   95.80 -61.00-150.00   74
 28  \w      8.00 107.00   0.50    0.70    --   95.80 -61.00  30.00  198
 29  \w     76.00 102.00   0.50    0.70    --   95.80  62.00-132.22   52
 30  \w    160.00 185.00   0.50    0.70    --   95.80  61.00  90.00   50
 31  \w    114.00 156.00   0.50    0.70    --   95.80  61.00  90.00   84
 32  \w     73.00 106.00   0.50    0.70    --   95.80  61.00  90.00   66
 33  \w    134.00 182.00   0.50    0.70    --   95.80  61.00 -60.00   96
 34  \w     73.00 127.00   0.50    0.70    --   95.80  61.00 -60.00  108
 35  \w      6.00  83.00   0.50    0.70    --   95.80 -61.00 -60.00  154
 36  \w     79.00 133.00   0.50    0.70    --   95.80  77.00-180.00  108
 37  \w    143.00 170.00   0.50    0.70    --   95.80  61.00 120.00   54
 38  \w     34.00 121.00   0.50    0.70    --   95.80 -82.00-150.00  174
 39  \w     72.00 150.00   0.50    0.70    --   95.80  61.00 150.00  156
 40  \w     72.00 124.00   0.50    0.70    --   95.80  61.00 120.00  104
 41  \w     73.00 136.00   0.50    0.70    --   95.80  61.00  60.00  126
 42  \w    131.00 185.00   0.50    0.70    --   95.80  30.00  60.00  108
 43  \w     72.00 156.00   0.50    0.70    --   95.80  61.00 -90.00  168
 44  \w     73.00 133.00   0.50    0.70    --   95.80  61.00-180.00  120
 45  \w     81.00 123.00   0.50    0.70    --   95.80  30.00  60.00   84
;
_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      0.1261171000
_diffrn_orient_matrix_UB_12      -0.1035212000
_diffrn_orient_matrix_UB_13      0.0687286000
_diffrn_orient_matrix_UB_21      -0.0465113000
_diffrn_orient_matrix_UB_22      0.0336707000
_diffrn_orient_matrix_UB_23      0.1330794000
_diffrn_orient_matrix_UB_31      -0.1744254000
_diffrn_orient_matrix_UB_32      -0.1111894000
_diffrn_orient_matrix_UB_33      -0.0344497000
_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  0.0259
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            21601
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.479
_diffrn_reflns_theta_min         4.411
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'MicroMax 007 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.327
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78889
_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    1.317
_exptl_crystal_description       block
_exptl_crystal_F_000             300
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2514 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     364
_refine_ls_number_reflns         5516
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0301
_refine_ls_R_factor_gt           0.0294
_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^)+(0.0434P)^2^+0.1471P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0770
_reflns_Friedel_coverage         0.912
_reflns_Friedel_fraction_full    0.949
_reflns_Friedel_fraction_max     0.887
_reflns_number_gt                5406
_reflns_number_total             5516
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02347e2.cif
_cod_data_source_block           fck37pc7_collect
_cod_depositor_comments
'Adding full bibliography for 7134660--7134669.cif.'
_cod_database_code               7134665
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H14 N14 O14 '
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.752
_reflns_odcompleteness_completeness 99.61
_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:
 C7(H7), C6(H6), C8(H8), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C18(H18), C30(H30), C29(H29), C32(H32), C27(H27), C15(H15), C33(H33),
 C23(H23), C16(H16), C17(H17), C26(H26), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C38(H38A,H38B,H38C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              43148
_shelx_hkl_checksum              25865
_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 1.519
_oxdiff_exptl_absorpt_empirical_full_min 0.563