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_7134660
_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 block
_chemical_formula_moiety         'C31 H17 Br Cl2 O2'
_chemical_formula_sum            'C31 H17 Br Cl2 O2'
_chemical_formula_weight         572.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-01-27 deposited with the CCDC.	2025-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.4170(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   43.9803(4)
_cell_length_b                   8.17570(10)
_cell_length_c                   14.36050(10)
_cell_measurement_reflns_used    22766
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      74.1860
_cell_measurement_theta_min      3.1400
_cell_volume                     4977.80(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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   -108.00 -13.00   1.00    2.00    --  -41.14 -57.00   0.00   95
  2  \w    -53.00  -9.00   1.00    2.00    --  -41.14 -77.00  60.00   44
  3  \w    -95.00 -12.00   1.00    2.00    --  -41.14 -77.00 -30.00   83
  4  \w   -117.00  -9.00   1.00    2.00    --  -41.14 -77.00 150.00  108
  5  \w    -84.00 -17.00   1.00    2.00    --  -41.14 -38.00-150.00   67
  6  \w    -69.00  32.00   1.00    2.00    --  -41.14  57.00  30.00  101
  7  \w   -103.00  -9.00   1.00    2.00    --  -41.14 -77.00-120.00   94
  8  \w    -69.00  32.00   1.00    2.00    --  -41.14  57.00 150.00  101
  9  \w    -64.00  28.00   1.00    2.00    --  -41.14  57.00 -90.00   92
 10  \w     48.00  82.00   1.00    2.00    --   41.14 -99.00 120.00   34
 11  \w     79.00 105.00   1.00    8.00    --  107.79  61.00   0.00   26
 12  \w     75.00 102.00   1.00    8.00    --  107.79  77.00  30.00   27
 13  \w     75.00 101.00   1.00    8.00    --  107.79  77.00 -60.00   26
 14  \w     79.00 174.00   1.00    8.00    --  107.79  61.00 -90.00   95
 15  \w     75.00 177.00   1.00    8.00    --  107.79  77.00  60.00  102
 16  \w    110.00 178.00   1.00    8.00    --  107.79  77.00   0.00   68
 17  \w    112.00 171.00   1.00    8.00    --  107.79  77.00-180.00   59
 18  \w     75.00 101.00   1.00    8.00    --  107.79  77.00-180.00   26
 19  \w     79.00 175.00   1.00    8.00    --  107.79  61.00 -60.00   96
 20  \w    138.00 172.00   1.00    8.00    --  107.79  61.00-120.00   34
 21  \w     40.00 140.00   1.00    8.00    --  107.79 -77.00   0.00  100
 22  \w     75.00 101.00   1.00    8.00    --  107.79  77.00   0.00   26
 23  \w     75.00 171.00   1.00    8.00    --  107.79  77.00 120.00   96
 24  \w     79.00 105.00   1.00    8.00    --  107.79  61.00-120.00   26
 25  \w     79.00 118.00   1.00    8.00    --  107.79-125.00-180.00   39
 26  \w     80.00 109.00   1.00    8.00    --  107.79  61.00-150.00   29
 27  \w     79.00 140.00   1.00    8.00    --  107.79  61.00 120.00   61
 28  \w     80.00 105.00   1.00    8.00    --  107.79  61.00 -30.00   25
 29  \w     79.00 159.00   1.00    8.00    --  107.79  61.00  60.00   80
 30  \w     79.00 105.00   1.00    8.00    --  107.79  61.00-180.00   26
 31  \w     79.00 105.00   1.00    8.00    --  107.79  61.00  90.00   26
 32  \w     79.00 106.00   1.00    8.00    --  107.79  61.00 150.00   27
 33  \w     75.00 101.00   1.00    8.00    --  107.79  77.00  90.00   26
 34  \w     75.00 101.00   1.00    8.00    --  107.79  77.00 -90.00   26
 35  \w     75.00 101.00   1.00    8.00    --  107.79  77.00-120.00   26
 36  \w     75.00 174.00   1.00    8.00    --  107.79  77.00 -30.00   99
 37  \w     33.00 140.00   1.00    8.00    --  107.79 -77.00 150.00  107
 38  \w     79.00 105.00   1.00    8.00    --  107.79  61.00  30.00   26
 39  \w     75.00 178.00   1.00    8.00    --  107.79  77.00-150.00  103
 40  \w     35.00 118.00   1.00    8.00    --  107.79-125.00   0.00   83
 41  \w     75.00 170.00   1.00    8.00    --  107.79  77.00 150.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0100628581
_diffrn_orient_matrix_UB_12      -0.0246003005
_diffrn_orient_matrix_UB_13      0.0939438350
_diffrn_orient_matrix_UB_21      -0.0330607147
_diffrn_orient_matrix_UB_22      0.0668938674
_diffrn_orient_matrix_UB_23      -0.0500550864
_diffrn_orient_matrix_UB_31      -0.0112406571
_diffrn_orient_matrix_UB_32      -0.1743776025
_diffrn_orient_matrix_UB_33      -0.0324901247
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -54
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            37893
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.189
_diffrn_reflns_theta_min         3.192
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.450
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29118
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_description       block
_exptl_crystal_F_000             2304
_refine_diff_density_max         0.639
_refine_diff_density_min         -0.925
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 3893 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.016(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     649
_refine_ls_number_reflns         9656
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.163
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0386
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0619P)^2^+2.4178P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1032
_refine_ls_wR_factor_ref         0.1051
_reflns_Friedel_coverage         0.784
_reflns_Friedel_fraction_full    0.927
_reflns_Friedel_fraction_max     0.903
_reflns_number_gt                9303
_reflns_number_total             9656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02347e2.cif
_cod_data_source_block           a21021301a0375
_cod_depositor_comments
'Adding full bibliography for 7134660--7134669.cif.'
_cod_database_code               7134660
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CHOClBr
_chemical_oxdiff_usercomment     FKO38+A11
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Br01-O008
 3.5 with sigma of 0.01
3.a Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00H(H00H), C00L(H00L), C00N(H00N), C00P(H00P), C00Q(H00Q),
 C00T(H00T), C00W(H00W), C011(H011), C012(H012), C014(H014), C015(H015),
 C016(H016), C017(H017), C01D(H01D), C01F(H01F), C01G(H01G), C01H(H01H),
 C01I(H01I), C01J(H01J), C01K(H01K), C01L(H01L), C01M(H01M), C01N(H01N),
 C01O(H01O), C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S), C01T(H01T),
 C01U(H01U), C01V(H01V), C01W(H01W), C01Y(H01Y)
;
_shelx_res_checksum              11327
_shelx_hkl_checksum              17044
_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 2.281
_oxdiff_exptl_absorpt_empirical_full_min 0.356