Enantioselective [3+2]-cycloaddition of 2,3-disubstituted cyclobutenones: vicinal quaternary stereocenters construction and skeletal functionalization.
Lu, Licheng; Lu, Ping; Chemical science 14 (2023) 8355–8359; doi:10.1039/d3sc02485g

data_1569544
_publ_section_title
;
 Enantioselective [3+2]-cycloaddition of 2,3-disubstituted cyclobutenones:
 vicinal quaternary stereocenters construction and skeletal
 functionalization.
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              8355
_journal_page_last               8359
_journal_paper_doi               10.1039/d3sc02485g
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C30 H31 N O8 S'
_chemical_formula_sum            'C30 H31 N O8 S'
_chemical_formula_weight         565.62
_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_block_doi                 10.5517/ccdc.csd.cc2fz2k2
_audit_creation_date             2023-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-05-16 deposited with the CCDC.	2023-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.2370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.63180(10)
_cell_length_b                   7.14960(10)
_cell_length_c                   15.68420(10)
_cell_measurement_reflns_used    24674
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      74.2020
_cell_measurement_theta_min      3.5720
_cell_volume                     1389.32(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      173.00(10)
_diffrn_detector                 'CCD plate'
_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      7.00  87.00   1.00    1.00    --    0.00  77.00-120.00   80
  2  \w    -24.00  81.00   1.00    1.00    --    0.00  19.00  30.00  105
  3  \w     -6.00  19.00   1.00    1.00    --    0.00 -37.00 -90.00   25
  4  \w     45.00  72.00   1.00    1.00    --    0.00  37.00 120.00   27
  5  \w     40.00  78.00   1.00    1.00    --    0.00  57.00-150.00   38
  6  \w     59.00  84.00   1.00    1.00    --    0.00  37.00-180.00   25
  7  \w     31.00  57.00   1.00    1.00    --    0.00  37.00-180.00   26
  8  \w     29.00  60.00   1.00    1.00    --    0.00  57.00  30.00   31
  9  \w    -44.00  -9.00   1.00    1.00    --    0.00 -82.00-120.00   35
 10  \w    -19.00  26.00   1.00    1.00    --    0.00  37.00 120.00   45
 11  \w    -88.00 -48.00   1.00    1.00    --    0.00 -82.00-120.00   40
 12  \w    -56.00 -25.00   1.00    1.00    --    0.00 -37.00 -90.00   31
 13  \w    -21.00  13.00   1.00    1.00    --    0.00  57.00  30.00   34
 14  \w    -23.00  33.00   1.00    1.00    --    0.00  57.00-150.00   56
 15  \w     68.00  93.00   1.00    1.00    --   95.80  70.00  98.18   25
 16  \w    136.00 185.00   1.00    1.00    --   95.80  74.00 -87.31   49
 17  \w     71.00 185.00   1.00    1.00    --   95.80  61.00  63.85  114
 18  \w     66.00 123.00   1.00    1.00    --   95.80  74.00 -87.31   57
 19  \w      6.00 128.00   1.00    1.00    --   95.80 -82.00 131.81  122
 20  \w     71.00 180.00   1.00    1.00    --   95.80  63.00 129.34  109
 21  \w    109.00 167.00   1.00    1.00    --   95.80  63.00-137.48   58
 22  \w     72.00 120.00   1.00    1.00    --   95.80  61.00  90.00   48
 23  \w     48.00 117.00   1.00    1.00    --   95.80 -82.00-150.00   69
 24  \w     63.00 124.00   1.00    1.00    --   95.80  82.00 150.00   61
 25  \w     63.00 103.00   1.00    1.00    --   95.80  82.00-120.00   40
 26  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -30.00   25
 27  \w    112.00 138.00   1.00    1.00    --   95.80  77.00 -30.00   26
 28  \w     66.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   25
 29  \w    100.00 126.00   1.00    1.00    --   95.80  77.00 -60.00   26
 30  \w     64.00  90.00   1.00    1.00    --   95.80  82.00   0.00   26
 31  \w     68.00  93.00   1.00    1.00    --   95.80  68.00-119.09   25
 32  \w      6.00 125.00   1.00    1.00    --   95.80 -82.00  30.00  119
 33  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 34  \w     70.00  96.00   1.00    1.00    --   95.80  63.00   3.64   26
 35  \w    142.00 167.00   1.00    1.00    --   95.80  54.00  23.89   25
 36  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 37  \w      6.00 120.00   1.00    1.00    --   95.80 -61.00 -90.00  114
 38  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 120.00   25
 39  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 40  \w    115.00 142.00   1.00    1.00    --   95.80  81.00 137.48   27
 41  \w     66.00  91.00   1.00    1.00    --   95.80  77.00-180.00   25
 42  \w     62.00 121.00   1.00    1.00    --   95.80 -77.00  60.00   59
 43  \w     72.00  98.00   1.00    1.00    --   95.80  61.00 120.00   26
 44  \w     65.00  91.00   1.00    1.00    --   95.80  82.00 -90.00   26
 45  \w     71.00 185.00   1.00    1.00    --   95.80  61.00 -30.00  114
 46  \w     71.00  96.00   1.00    1.00    --   95.80  61.00-150.00   25
 47  \w     71.00 167.00   1.00    1.00    --   95.80  61.00-120.00   96
 48  \w     71.00 139.00   1.00    1.00    --   95.80  61.00   0.00   68
 49  \w     71.00 124.00   1.00    1.00    --   95.80  61.00  30.00   53
 50  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 51  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 52  \w    123.00 180.00   1.00    1.00    --   95.80  82.00   0.00   57
 53  \w     58.00 124.00   1.00    1.00    --   95.80 -82.00 -60.00   66
 54  \w     75.00 100.00   1.00    1.00    --   95.80  45.00 -30.00   25
 55  \w     75.00 124.00   1.00    1.00    --   95.80  45.00 120.00   49
 56  \w    130.00 158.00   1.00    1.00    --   95.80  45.00 120.00   28
 57  \w     64.00  90.00   1.00    1.00    --   95.80  81.00 137.48   26
 58  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 59  \w     73.00  98.00   1.00    1.00    --   95.80  54.00  23.89   25
 60  \w     70.00 106.00   1.00    1.00    --   95.80  63.00-137.48   36
 61  \w     72.00 183.00   1.00    1.00    --   95.80  55.00-157.61  111
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1068932000
_diffrn_orient_matrix_UB_12      0.1067559000
_diffrn_orient_matrix_UB_13      0.0291519000
_diffrn_orient_matrix_UB_21      0.0089914000
_diffrn_orient_matrix_UB_22      -0.0778725000
_diffrn_orient_matrix_UB_23      0.0927124000
_diffrn_orient_matrix_UB_31      0.0628761000
_diffrn_orient_matrix_UB_32      -0.1702315000
_diffrn_orient_matrix_UB_33      -0.0241500000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            29729
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.069
_diffrn_reflns_theta_max         67.069
_diffrn_reflns_theta_min         2.872
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.482
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78366
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.352
_exptl_crystal_description       block
_exptl_crystal_F_000             596
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.191
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 2223 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(6)
_refine_ls_extinction_coef       0.0060(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         4977
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0242
_refine_ls_R_factor_gt           0.0240
_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^)+(0.0347P)^2^+0.2619P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0628
_refine_ls_wR_factor_ref         0.0631
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                4926
_reflns_number_total             4977
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02485g2.cif
_cod_data_source_block           exp_3074
_cod_depositor_comments
'Adding full bibliography for 1569539--1569545.cif.'
_cod_database_code               1569544
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.682
_shelx_estimated_absorpt_t_min   0.596
_reflns_odcompleteness_completeness 100.00
_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.a Ternary CH refined with riding coordinates:
 C19(H19), C21(H21), C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C0AA(H0AA), C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C24(H24A,H24B,H24C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              60890
_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 2.016
_oxdiff_exptl_absorpt_empirical_full_min 0.644