Gold-Catalyzed [3 + 2] Annulation, Carbenoid Transfer, and C–H Insertion Cascade: Elucidation of Annulation Mechanisms via Benzopyrylium Intermediates
Koshikawa, Takumi; Nagashima, Yuki; Tanaka, Ken; ACS Catalysis  (2021) 1932–1937; doi:10.1021/acscatal.0c05394

data_4518429
_publ_section_title
;
 Gold-Catalyzed [3 + 2] Annulation, Carbenoid Transfer, and C--H Insertion
 Cascade: Elucidation of Annulation Mechanisms via Benzopyrylium
 Intermediates
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1932
_journal_page_last               1937
_journal_paper_doi               10.1021/acscatal.0c05394
_journal_year                    2021
_chemical_formula_moiety         'C H Cl3, C33 H28 O6'
_chemical_formula_sum            'C34 H29 Cl3 O6'
_chemical_formula_weight         639.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-17
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.03.30 svn.r3266 for Rigaku Oxford Diffraction, GUI svn.r5168)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.332(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1057(11)
_cell_length_b                   12.6770(16)
_cell_length_c                   24.493(3)
_cell_measurement_reflns_used    6987
_cell_measurement_temperature    293
_cell_measurement_theta_max      26.0720
_cell_measurement_theta_min      2.5940
_cell_volume                     3104.7(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.12b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.12b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.12b (Rigaku OD, 2015)'
_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_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.955
_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     44.00 109.50   0.50   75.00    --   20.00  54.00 150.00  131
  2  \w    -74.00  37.50   0.50   75.00    --   20.00  54.00 -90.00  223
  3  \w     58.00  90.50   0.50   75.00    --   20.00  54.00 -90.00   65
  4  \w    -74.00  28.50   0.50   75.00    --   20.00  54.00-150.00  205
  5  \w     51.00  98.50   0.50   75.00    --   20.00  54.00-150.00   95
  6  \w    -72.00 105.50   0.50   75.00    --   20.00  54.00-180.00  355
  7  \w    -55.00 -30.50   0.50   75.00    --   20.00  54.00  30.00   49
  8  \w     23.00  51.50   0.50   75.00    --   20.00  54.00  30.00   57
  9  \w     83.00 107.50   0.50   75.00    --   20.00  54.00  30.00   49
 10  \w    -71.00 -45.50   0.50   75.00    --   20.00  54.00 -30.00   51
 11  \w     80.00 104.50   0.50   75.00    --   20.00  54.00 -30.00   49
 12  \w    -71.00  30.50   0.50   75.00    --   20.00  54.00 150.00  203
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0040329000
_diffrn_orient_matrix_UB_12      0.0414188000
_diffrn_orient_matrix_UB_13      0.0196244000
_diffrn_orient_matrix_UB_21      0.0079359000
_diffrn_orient_matrix_UB_22      -0.0375728000
_diffrn_orient_matrix_UB_23      0.0216992000
_diffrn_orient_matrix_UB_31      0.0703879000
_diffrn_orient_matrix_UB_32      0.0017608000
_diffrn_orient_matrix_UB_33      0.0007294000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            40985
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.554
_diffrn_reflns_theta_min         2.325
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.340
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.12b (Rigaku Oxford Diffraction, 2015)
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    1.369
_exptl_crystal_description       block
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.692
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         9086
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1333
_refine_ls_R_factor_gt           0.0881
_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^)+(0.1245P)^2^+1.8126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2340
_refine_ls_wR_factor_ref         0.2661
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5671
_reflns_number_total             9086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c05394_si_002.cif
_cod_data_source_block           kt358f1
_cod_database_code               4518429
_chemical_oxdiff_formula         C39H27O6Cl3
_chemical_oxdiff_usercomment     rt
_reflns_odcompleteness_completeness 99.10
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Others
 Sof(H34A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=1-FVAR(1)
 Sof(Cl3)=Sof(Cl2)=Sof(Cl1)=Sof(H34)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C26(H26), C12(H12), C1(H1), C3(H3), C34(H34A), C34(H34)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C2(H2A,H2B)
3.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C23(H23), C31(H31), C20(H20), C29(H29), C30(H30), C5(H5), C7(H7),
 C22(H22), C21(H21), C6(H6)
3.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C)
;
_shelx_shelxl_version_number     2016/6
_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 1.209
_oxdiff_exptl_absorpt_empirical_full_min 0.860