Copper-catalyzed enantioselective diyne cyclization <i>via</i> C(sp<sup>2</sup>)-O bond cleavage.
Zhou, Ji-Jia; Meng, Ya-Nan; Liu, Li-Gao; Liu, Yi-Xi; Xu, Zhou; Lu, Xin; Zhou, Bo; Ye, Long-Wu; Chemical science 14 (2023) 3493–3500; doi:10.1039/d2sc06152j

data_1568543
_publ_section_title
;
 Copper-catalyzed enantioselective diyne cyclization <i>via</i>
 C(sp<sup>2</sup>)-O bond cleavage.
;
_journal_issue                   13
_journal_name_full               'Chemical science'
_journal_page_first              3493
_journal_page_last               3500
_journal_paper_doi               10.1039/d2sc06152j
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C25 H21 N O4 S'
_chemical_formula_sum            'C25 H21 N O4 S'
_chemical_formula_weight         431.49
_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             2022-05-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-07-27 deposited with the CCDC.	2023-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.8290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.18980(10)
_cell_length_b                   7.99840(10)
_cell_length_c                   14.9186(2)
_cell_measurement_reflns_used    8410
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.0040
_cell_measurement_theta_min      2.9560
_cell_volume                     1092.68(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.964
_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     86.00 134.00   0.50    0.50    --  109.59  61.00 150.00   96
  2  \w    140.00 177.00   0.50    0.50    --  109.59  30.00 -90.00   74
  3  \w    101.00 128.00   0.50    0.50    --  109.59  30.00 -90.00   54
  4  \w     39.00  73.00   0.50    0.50    --  109.59-125.00-150.00   68
  5  \w     89.00 115.00   0.50    0.50    --  109.59-125.00-150.00   52
  6  \w     68.00 108.00   0.50    0.50    --  109.59-125.00 -90.00   80
  7  \w     56.00 116.00   0.50    0.50    --  109.59-125.00 -30.00  120
  8  \w     39.00 108.00   0.50    0.50    --  109.59 -93.00 -12.00  138
  9  \w     36.00  80.00   0.50    0.50    --  109.59-125.00  90.00   88
 10  \w     88.00 115.00   0.50    0.50    --  109.59-125.00  90.00   54
 11  \w     18.00  52.00   0.50    0.10    --   43.09 -93.00 -12.00   68
 12  \w    -30.00  -1.00   0.50    0.10    --   43.09 -19.00 -30.00   58
 13  \w     46.00  73.00   0.50    0.50    --  109.59 -77.00  60.00   54
 14  \w     76.00 101.00   0.50    0.50    --  109.59 -77.00  60.00   50
 15  \w     37.00  66.00   0.50    0.50    --  109.59 -61.00 120.00   58
 16  \w     42.00  69.00   0.50    0.50    --  109.59 -61.00   0.00   54
 17  \w     38.00  68.00   0.50    0.50    --  109.59 -61.00 -90.00   60
 18  \w     39.00  73.00   0.50    0.50    --  109.59 -77.00-180.00   68
 19  \w     41.00  71.00   0.50    0.50    --  109.59 -61.00-180.00   60
 20  \w    -36.00  20.00   0.50    0.10    --   43.09 -19.00   0.00  112
 21  \w    139.00 164.00   0.50    0.50    --  109.59  93.00  99.00   50
 22  \w    100.00 141.00   0.50    0.50    --  109.59 125.00 -90.00   82
 23  \w    146.00 174.00   0.50    0.50    --  109.59 125.00 -90.00   56
 24  \w      0.00  27.00   0.50    0.10    --  -43.09  19.00-150.00   54
 25  \w    -48.00 -21.00   0.50    0.50    --  -96.00  45.00-120.00   54
 26  \w    -63.00 -30.00   0.50    0.50    --  -96.00  61.00 -60.00   66
 27  \w    -21.00  38.00   0.50    0.10    --  -43.09  19.00-120.00  118
 28  \w    -50.00 -19.00   0.50    0.50    --  -96.00  45.00   0.00   62
 29  \w    -55.00 -28.00   0.50    0.50    --  -96.00  61.00  30.00   54
 30  \w    -50.00 -19.00   0.50    0.50    --  -96.00  45.00  30.00   62
 31  \w    -48.00 -21.00   0.50    0.50    --  -96.00  45.00 120.00   54
 32  \w    -81.00  33.00   0.50    0.10    --  -43.09  93.00  99.00  228
 33  \w    -57.00 -21.00   0.50    0.50    --  -96.00 125.00  30.00   72
 34  \w    -79.00 -23.00   0.50    0.50    --  -96.00  93.00  99.00  112
 35  \w   -173.00 -81.00   0.50    0.50    --  -96.00 -45.00-120.00  184
 36  \w   -170.00 -70.00   0.50    0.50    --  -96.00 -61.00 -90.00  200
 37  \w   -128.00 -92.00   0.50    0.50    --  -96.00 -93.00 -12.00   72
 38  \w   -154.00 -72.00   0.50    0.50    --  -96.00 -61.00  30.00  164
 39  \w   -116.00 -33.00   0.50    0.10    --  -43.09 -77.00   0.00  166
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1009161000
_diffrn_orient_matrix_UB_12      0.1289913000
_diffrn_orient_matrix_UB_13      0.0400656000
_diffrn_orient_matrix_UB_21      0.0276189000
_diffrn_orient_matrix_UB_22      0.1231670000
_diffrn_orient_matrix_UB_23      -0.0761112000
_diffrn_orient_matrix_UB_31      -0.1316917000
_diffrn_orient_matrix_UB_32      -0.0729835000
_diffrn_orient_matrix_UB_33      -0.0577512000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0442
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            10508
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.086
_diffrn_reflns_theta_min         2.973
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.578
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.04179
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             452
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.373
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Flack x determined using 1766 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.013(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.167
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         4228
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0660P)^2^+0.4490P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1237
_refine_ls_wR_factor_ref         0.1248
_reflns_Friedel_coverage         0.814
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.912
_reflns_number_gt                4077
_reflns_number_total             4228
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06152j2.cif
_cod_data_source_block           exp_9980_auto
_cod_depositor_comments          'Adding full bibliography for 1568543.cif.'
_cod_database_code               1568543
_shelxl_version_number           2013-2
_diffrn_oxdiff_digest_frames
;
01f9a5bb0d4ded192a902e2c1330cdfdfd0004606f2
;
_diffrn_oxdiff_digest_hkl
;
01eb7af09155e05c013ec7c58d61f3756251d4
;
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
2.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              76072
_shelx_hkl_checksum              49504
_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 11.513
_oxdiff_exptl_absorpt_empirical_full_min 0.597