Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Constructions of Bicyclo[3.2.1]oct-6-ene Frameworks via (4 + 3)-Cycloadditions
Tanpure, Sudhakar Dattatray; Kuo, Tung-Chun; Cheng, Mu-Jeng; Liu, Rai-Shung; ACS Catalysis  (2021) 536–543; doi:10.1021/acscatal.1c04483

data_4519231
_publ_section_title
;
 Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Constructions of
 Bicyclo[3.2.1]oct-6-ene Frameworks via (4 + 3)-Cycloadditions
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              536
_journal_page_last               543
_journal_paper_doi               10.1021/acscatal.1c04483
_journal_year                    2021
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C35 H28 O'
_chemical_formula_sum            'C35 H28 O'
_chemical_formula_weight         464.57
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-06
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   21.1226(2)
_cell_length_b                   21.1226(2)
_cell_length_c                   10.92510(10)
_cell_measurement_reflns_used    31540
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.0170
_cell_measurement_theta_min      4.1460
_cell_volume                     4221.34(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.33a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.42.33a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.42.33a (Rigaku OD, 2021)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.976
_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     54.00 110.10   0.30    0.65    --   69.49  15.00  60.00  187
  2  \w     37.00  84.10   0.30    0.65    --   56.41  15.00  30.00  157
  3  \w     66.00  97.50   0.30    0.65    --   56.41  15.00 -30.00  105
  4  \w     47.00 116.90   0.30    0.65    --   76.49  15.00-120.00  233
  5  \w     48.00 117.00   0.30    0.65    --   76.49  15.00-180.00  230
  6  \w     88.00 113.80   0.30    0.65    --   76.49  15.00 -30.00   86
  7  \w     44.00  69.80   0.30    0.65    --   76.49  15.00 -30.00   86
  8  \w     50.00 105.20   0.30    0.65    --   76.49  15.00 120.00  184
  9  \w     25.00  57.10   0.30    0.65    --   56.41-125.00-180.00  107
 10  \w     42.00  96.00   0.30    0.65    --   80.36-112.00-130.92  180
 11  \w     20.00  50.00   0.30    0.65    --   56.41-125.00 -60.00  100
 12  \w     68.00  93.20   0.30    0.65    --   80.36-108.00 -94.64   84
 13  \w     43.00  91.00   0.30    0.65    --   76.49-111.00   0.00  160
 14  \w     46.00  96.10   0.30    0.65    --   80.00-111.00  22.64  167
 15  \w     20.00  63.20   0.30    0.65    --   56.41-125.00  30.00  144
 16  \w     24.00  49.80   0.30    0.65    --   56.41-125.00  90.00   86
 17  \w   -100.00 -43.00   0.30    0.65    --  -59.25 -15.00  90.00  190
 18  \w   -114.00 -54.00   0.30    0.65    --  -72.15 -15.00  30.00  200
 19  \w    -74.00 -47.00   0.30    0.65    --  -75.36 -15.00 -60.00   90
 20  \w   -120.00 -45.00   0.30    0.65    --  -75.36 -15.00 -90.00  250
 21  \w   -118.00 -82.00   0.30    0.65    --  -75.36 -15.00-180.00  120
 22  \w    -77.00 -44.00   0.30    0.65    --  -75.36 -15.00-180.00  110
 23  \w    -91.00 -37.00   0.30    0.65    --  -75.36 111.00-180.00  180
 24  \w    -97.00 -46.00   0.30    0.65    --  -80.00 115.00-127.32  170
 25  \w    -63.00 -18.00   0.30    0.65    --  -59.25 125.00 -30.00  150
 26  \w    -62.00 -37.10   0.30    0.65    --  -80.00 112.00-104.74   83
 27  \w    -91.00 -34.00   0.30    0.65    --  -75.36 111.00 -90.00  190
 28  \w    -67.00 -41.50   0.30    0.65    --  -75.36 111.00 -30.00   85
 29  \w    -91.00 -43.00   0.30    0.65    --  -75.36 111.00   0.00  160
 30  \w    -61.00 -35.20   0.30    0.65    --  -75.36 111.00  30.00   86
 31  \w    -97.00 -40.00   0.30    0.65    --  -80.00 114.00  41.27  190
 32  \w    -97.00 -61.00   0.30    0.65    --  -80.00 114.00  92.05  120
 33  \w    -48.00 -15.00   0.30    0.65    --  -59.25 125.00 150.00  110
 34  \w    -96.00 -36.00   0.30    0.65    --  -80.00 111.00 137.62  200
 35  \w    -83.00 -44.00   0.30    0.65    --  -75.36 111.00  90.00  130
 36  \w    -64.00 -37.00   0.30    0.65    --  -75.36 111.00 120.00   90
 37  \w    -96.00 -43.80   0.30    0.65    --  -80.00 111.00  66.60  174
 38  \w    -72.00 -33.00   0.30    0.65    --  -75.36 111.00-150.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0822609000
_diffrn_orient_matrix_UB_12      0.0408102000
_diffrn_orient_matrix_UB_13      -0.0301821000
_diffrn_orient_matrix_UB_21      0.0008306000
_diffrn_orient_matrix_UB_22      0.0733217000
_diffrn_orient_matrix_UB_23      0.0033871000
_diffrn_orient_matrix_UB_31      0.0179769000
_diffrn_orient_matrix_UB_32      0.0071262000
_diffrn_orient_matrix_UB_33      0.1377271000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            56811
_diffrn_reflns_point_group_measured_fraction_full 0.878
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.094
_diffrn_reflns_theta_min         4.186
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.493
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87531
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.33a (Rigaku Oxford Diffraction, 2021)
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    1.096
_exptl_crystal_description       needle
_exptl_crystal_F_000             1476
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.170
_refine_diff_density_min         -0.118
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.1(3)
_refine_ls_extinction_coef       0.00141(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         4767
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0281
_refine_ls_R_factor_gt           0.0272
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0510P)^2^+0.2000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0745
_reflns_Friedel_coverage         0.639
_reflns_Friedel_fraction_full    0.742
_reflns_Friedel_fraction_max     0.697
_reflns_number_gt                4625
_reflns_number_total             4767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04483_si_006.cif
_cod_data_source_block           211213lt_auto
_cod_original_cell_volume        4221.34(9)
_cod_database_code               4519231
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.895
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9(3)
 0.1(3)
2. 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
3.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20),
 C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29),
  C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
3.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              63055
_shelx_hkl_checksum              3117
_shelx_fab_checksum              69747
_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 1.575
_oxdiff_exptl_absorpt_empirical_full_min 0.580