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_4519236
_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         'C31 H28 O'
_chemical_formula_sum            'C31 H28 O'
_chemical_formula_weight         416.53
_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     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                 108.646(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4891(6)
_cell_length_b                   10.8641(4)
_cell_length_c                   18.4420(8)
_cell_measurement_reflns_used    18405
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      72.9850
_cell_measurement_theta_min      3.6490
_cell_volume                     2370.92(19)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     27.00  58.50   0.30    0.41    --   57.89-125.00   0.00  105
  2  \w     36.00 102.00   0.30    0.41    --   78.57-128.00-106.32  220
  3  \w     49.00 101.20   0.30    0.41    --   78.57-127.00 -17.82  174
  4  \w     38.00  62.90   0.30    0.41    --   78.57-106.00  30.37   83
  5  \w     45.00 102.00   0.30    0.41    --   78.57-128.00 168.79  190
  6  \w   -105.00 -45.00   0.30    0.41    --  -60.97 -15.00-150.00  200
  7  \w   -105.00 -45.90   0.30    0.41    --  -60.97 -15.00 -90.00  197
  8  \w    -78.00 -48.00   0.30    0.41    --  -60.97 -15.00 -60.00  100
  9  \w    -98.00 -57.80   0.30    0.41    --  -73.68 -15.00 -90.00  134
 10  \w   -104.00 -69.20   0.30    0.41    --  -60.97 -15.00   0.00  116
 11  \w   -118.00 -80.20   0.30    0.41    --  -73.68 -15.00  30.00  126
 12  \w    -96.00 -45.00   0.30    0.41    --  -60.97 -15.00 150.00  170
 13  \w   -119.00 -59.00   0.30    0.41    --  -74.02 -15.00 120.00  200
 14  \w   -102.00 -58.80   0.30    0.41    --  -73.68 -15.00  60.00  144
 15  \w    -99.00 -48.00   0.30    0.41    --  -60.97 -15.00  30.00  170
 16  \w   -117.00 -57.00   0.30    0.41    --  -74.02 -15.00 -30.00  200
 17  \w   -119.00 -68.00   0.30    0.41    --  -74.02 -15.00-120.00  170
 18  \w   -118.00 -79.00   0.30    0.41    --  -73.68 -15.00-180.00  130
 19  \w    -96.00 -39.00   0.30    0.41    --  -78.57 116.00-140.87  190
 20  \w    -90.00 -30.90   0.30    0.41    --  -73.68 125.00-150.00  197
 21  \w    -73.00 -43.00   0.30    0.41    --  -73.68 125.00   0.00  100
 22  \w    -95.00 -35.00   0.30    0.41    --  -73.68 125.00  60.00  200
 23  \w    -79.00 -46.00   0.30    0.41    --  -73.68 125.00 120.00  110
 24  \w    -72.00 -39.00   0.30    0.41    --  -78.57 134.00  93.19  110
 25  \w    -50.00 -23.00   0.30    0.41    --  -60.97 125.00  90.00   90
 26  \w    -80.00 -53.00   0.30    0.41    --  -73.68 125.00  30.00   90
 27  \w    -96.00 -30.90   0.30    0.41    --  -74.02 125.00 -60.00  217
 28  \w    -70.00 -44.50   0.30    0.41    --  -78.57 123.00 -74.85   85
 29  \w    -70.00 -43.00   0.30    0.41    --  -73.68 125.00-180.00   90
 30  \w   -100.00 -73.00   0.30    0.41    --  -78.57 123.00 -74.85   90
 31  \w    -96.00 -45.00   0.30    0.41    --  -78.57 119.00 -17.67  170
 32  \w    -62.00 -36.20   0.30    0.41    --  -78.00 120.00  25.32   86
 33  \w    -97.00 -65.20   0.30    0.41    --  -78.00 120.00  25.32  106
 34  \w    -97.00 -70.00   0.30    0.41    --  -78.57 117.00 125.21   90
;
_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      -0.0761621000
_diffrn_orient_matrix_UB_12      -0.0299813000
_diffrn_orient_matrix_UB_13      -0.0819647000
_diffrn_orient_matrix_UB_21      -0.0977598000
_diffrn_orient_matrix_UB_22      -0.0323631000
_diffrn_orient_matrix_UB_23      0.0306789000
_diffrn_orient_matrix_UB_31      -0.0405002000
_diffrn_orient_matrix_UB_32      0.1345526000
_diffrn_orient_matrix_UB_33      -0.0109177000
_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  0.0515
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26227
_diffrn_reflns_point_group_measured_fraction_full 0.866
_diffrn_reflns_point_group_measured_fraction_max 0.866
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         2.529
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.525
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80669
_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    1.167
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.484
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.108
_refine_ls_abs_structure_details
;
 Flack x determined using 2613 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(3)
_refine_ls_extinction_coef       0.0028(6)
_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   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         7307
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0662
_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^)+(0.1171P)^2^+3.0150P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2052
_refine_ls_wR_factor_ref         0.2060
_reflns_Friedel_coverage         0.641
_reflns_Friedel_fraction_full    0.718
_reflns_Friedel_fraction_max     0.718
_reflns_number_gt                7043
_reflns_number_total             7307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04483_si_004.cif
_cod_data_source_block           211214lt_auto
_cod_depositor_comments
;

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C62 H56 O2'
_cod_original_formula_weight         833.06
_cod_original_formula_moiety         '2(C31 H28 O)'
_cod_original_formula_units_Z            2
_cod_database_code               4519236
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N '
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.945
_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:
 C3(H3), C35(H35)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C61(H61A,H61B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C19(H19), C20(H20),
 C21(H21), C22(H22), C23(H23), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
  C38(H38), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C50(H50),
 C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C62(H62A,H62B,
 H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              53226
_shelx_hkl_checksum              7763
_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 2.450
_oxdiff_exptl_absorpt_empirical_full_min 0.666