Catalytic asymmetric aromatizing inverse electron-demand [4+2] cycloaddition of 1-thioaurones and 1-azaaurones
Yuan, Shu-Pei; Dou, Pei-Hao; Jia, Yun-Qing; Zhao, Jian-Qiang; You, Yong; Wang, Zhen-Hua; Zhou, Ming-Qiang; Yuan, Weicheng; Chemical Communications  (2021) –; doi:10.1039/D1CC06357J

data_7129370
_publ_section_title
;
 Catalytic asymmetric aromatizing inverse electron-demand [4+2]
 cycloaddition of 1-thioaurones and 1-azaaurones
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06357J
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H29 N O5 S'
_chemical_formula_sum            'C34 H29 N O5 S'
_chemical_formula_weight         563.64
_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     iterative
_audit_creation_date             2021-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-09-23 deposited with the CCDC.	2021-12-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.280(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2382(4)
_cell_length_b                   18.0725(7)
_cell_length_c                   15.2764(5)
_cell_measurement_reflns_used    5846
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.7780
_cell_measurement_theta_min      3.9220
_cell_volume                     3094.02(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -57.00 -32.00   1.00    2.00    --  -33.50 178.00-150.00   25
  2  \w    -79.00  -1.00   1.00    2.00    --  -33.50 -19.00 120.00   78
  3  \w    -67.00 -41.00   1.00    2.00    --  -33.50 178.00 120.00   26
  4  \w    -55.00  37.00   1.00    2.00    --  -33.50  37.00 150.00   92
  5  \w     -4.00  70.00   1.00    2.00    --   36.47 -99.00 150.00   74
  6  \w     37.00 106.00   1.00    2.00    --   36.47  77.00-120.00   69
  7  \w     28.00  80.00   1.00    2.00    --   36.47  57.00 120.00   52
  8  \w     60.00 107.00   1.00    2.00    --   36.47 178.00 -30.00   47
  9  \w     42.00  89.00   1.00    2.00    --   36.47  77.00 150.00   47
 10  \w     27.00  64.00   1.00    2.00    --   36.47 -77.00 150.00   37
 11  \w     15.00 105.00   1.00    2.00    --   36.47  37.00 120.00   90
 12  \w     21.00  68.00   1.00    2.00    --   36.47  57.00 -60.00   47
 13  \w     40.00  77.00   1.00    2.00    --   36.47  57.00   0.00   37
 14  \w     -1.00  77.00   1.00    2.00    --   36.47 -99.00 -30.00   78
 15  \w     45.00 125.00   1.00    8.00    --  108.00 -30.00  30.00   80
 16  \w     38.00 109.00   1.00    8.00    --  108.00 -94.00-120.00   71
 17  \w     38.00 124.00   1.00    8.00    --  108.00 -45.00-150.00   86
 18  \w     50.00  76.00   1.00    8.00    --  108.00 -94.00 150.00   26
 19  \w     81.00 111.00   1.00    8.00    --  108.00-111.00   0.00   30
 20  \w     45.00 133.00   1.00    8.00    --  108.00 -30.00 -60.00   88
 21  \w     67.00 136.00   1.00    8.00    --  108.00 -77.00 -90.00   69
 22  \w     74.00 125.00   1.00    8.00    --  108.00  15.00  30.00   51
 23  \w     91.00 117.00   1.00    8.00    --  108.00 -45.00 -60.00   26
 24  \w     40.00  66.00   1.00    8.00    --  108.00 -45.00 -60.00   26
 25  \w     84.00 157.00   1.00    8.00    --  108.00  77.00   0.00   73
 26  \w     41.00 128.00   1.00    8.00    --  108.00 -61.00  30.00   87
 27  \w    109.00 135.00   1.00    8.00    --  108.00 101.00-175.00   26
 28  \w     66.00 110.00   1.00    8.00    --  108.00-101.00  80.00   44
 29  \w     41.00 111.00   1.00    8.00    --  108.00-111.00-150.00   70
 30  \w     82.00 153.00   1.00    8.00    --  108.00  30.00 -60.00   71
 31  \w     37.00 124.00   1.00    8.00    --  108.00 -30.00 120.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1037146000
_diffrn_orient_matrix_UB_12      -0.0545831000
_diffrn_orient_matrix_UB_13      -0.0088336000
_diffrn_orient_matrix_UB_21      0.0895716000
_diffrn_orient_matrix_UB_22      0.0601387000
_diffrn_orient_matrix_UB_23      0.0329774000
_diffrn_orient_matrix_UB_31      -0.0104767000
_diffrn_orient_matrix_UB_32      -0.0259320000
_diffrn_orient_matrix_UB_33      0.0951987000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0441
_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       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            23685
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.056
_diffrn_reflns_theta_max         67.056
_diffrn_reflns_theta_min         3.795
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.259
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91868
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.210
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 3271 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         11060
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0714
_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^)+(0.1399P)^2^+0.2605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2003
_refine_ls_wR_factor_ref         0.2200
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                8844
_reflns_number_total             11060
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06357j2.cif
_cod_data_source_block           202109228
_cod_original_cell_volume        3094.0(2)
_cod_database_code               7129370
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O2N2S1
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.834
_reflns_odcompleteness_completeness 99.95
_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. Restrained distances
 C22'-C26'
 1.55 with sigma of 0.02
 C1A-C24'
 1.55 with sigma of 0.02
 C32-C31
 1.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C17') \\sim Ueq, Uanis(C16') \\sim Ueq, Uanis(C19') \\sim Ueq,
Uanis(C18') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C27') \\sim Ueq, Uanis(C1B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C26') = Uanis(C1A)
Uanis(C27') = Uanis(C1B)
4. Others
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=
 Sof(H22')=1-FVAR(1)
 Sof(H24')=Sof(C26')=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27')=Sof(H27A)=
 Sof(H27B)=Sof(H27C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C9'(H9'), C10'(H10'), C9(H9), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C12'(H12A,H12B), C12(H12C,H12D)
5.c Aromatic/amide H refined with riding coordinates:
 C2'(H2'), C3'(H3'), C4'(H4'), C1'(H1'), C19'(H19'), C18'(H18'), C17'(H17'),
 C16'(H16'), C15'(H15'), C22'(H22'), C21'(H21'), C25'(H25'), C24'(H24'),
 C29'(H29'), C30'(H30'), C32'(H32'), C33'(H33'), C4(H4), C3(H3), C2(H2), C1(H1),
  C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C25(H25),
 C24(H24), C33(H33), C29(H29), C30(H30), C32(H32)
5.d Fitted hexagon refined as free rotating group:
 C2'(C3',C4',C5',C6',C1'), C14'(C19',C18',C17',C16',C15'), C23'(C22',C21',C20',
 C25',C24'), C28'(C29',C30',C31',C32',C33'), C6(C5,C4,C3,C2,C1), C14(C15,C16,
 C17,C18,C19), C22(C21,C20,C25,C24,C23), C33(C28,C29,C30,C31,C32)
5.e Idealised Me refined as rotating group:
 C1B(H1BA,H1BB,H1BC), C1A(H1AA,H1AB,H1AC), C26'(H26A,H26B,H26C), C27'(H27A,
 H27B,H27C), C34'(H34A,H34B,H34C), C26(H26D,H26E,H26F), C27(H27D,H27E,H27F),
 C34(H34D,H34E,H34F)
;
_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 1.212
_oxdiff_exptl_absorpt_empirical_full_min 0.851