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_1569543
_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         'C34 H39 N O6 Si'
_chemical_formula_sum            'C34 H39 N O6 Si'
_chemical_formula_weight         585.75
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2fz2fy
_audit_creation_date             2023-03-29
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.65320(10)
_cell_length_b                   12.55440(10)
_cell_length_c                   25.5448(3)
_cell_measurement_reflns_used    46200
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      74.2520
_cell_measurement_theta_min      3.4180
_cell_volume                     3095.78(5)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -10.00  16.00   1.00    1.00    --    0.00  29.00 135.00   26
  2  \w     28.00  54.00   1.00    1.00    --    0.00  29.00 135.00   26
  3  \w     76.00 185.00   1.00    1.00    --   95.80  29.00 135.00  109
  4  \w     60.00 109.00   1.00    1.00    --   95.80 -29.00 -25.00   49
  5  \w    -30.00   2.00   1.00    1.00    --    0.00  77.00  30.00   32
  6  \w     -9.00  17.00   1.00    1.00    --    0.00  57.00-150.00   26
  7  \w    -88.00 -32.00   1.00    1.00    --    0.00 -77.00 150.00   56
  8  \w    -21.00  88.00   1.00    1.00    --    0.00  57.00 150.00  109
  9  \w     11.00  37.00   1.00    1.00    --    0.00  77.00  30.00   26
 10  \w     20.00  75.00   1.00    1.00    --    0.00  57.00-150.00   55
 11  \w    -24.00   2.00   1.00    1.00    --    0.00  19.00 120.00   26
 12  \w    -26.00  29.00   1.00    1.00    --    0.00 -77.00 150.00   55
 13  \w     50.00  89.00   1.00    1.00    --    0.00  77.00-120.00   39
 14  \w    -89.00 -27.00   1.00    1.00    --    0.00 -57.00 -90.00   62
 15  \w    -19.00  16.00   1.00    1.00    --    0.00 -57.00 -90.00   35
 16  \w    -24.00  19.00   1.00    1.00    --    0.00 -37.00-150.00   43
 17  \w     38.00  82.00   1.00    1.00    --    0.00  37.00-120.00   44
 18  \w     20.00  47.00   1.00    1.00    --    0.00  77.00-120.00   27
 19  \w    -89.00 -43.00   1.00    1.00    --    0.00 -37.00-150.00   46
 20  \w     10.00  46.00   1.00    1.00    --    0.00  19.00 120.00   36
 21  \w    -56.00  19.00   1.00    1.00    --    0.00 -29.00 -25.00   75
 22  \w    -13.00  14.00   1.00    1.00    --    0.00  37.00-120.00   27
 23  \w     68.00  94.00   1.00    1.00    --   95.80  76.00 -97.88   26
 24  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 25  \w     78.00 128.00   1.00    1.00    --   95.80 -82.00 -60.00   50
 26  \w    160.00 185.00   1.00    1.00    --   95.80  82.00-180.00   25
 27  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -90.00   25
 28  \w     92.00 128.00   1.00    1.00    --   95.80 -82.00-120.00   36
 29  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 30  \w     74.00 123.00   1.00    1.00    --   95.80  50.00-155.11   49
 31  \w    126.00 171.00   1.00    1.00    --   95.80  50.00-155.11   45
 32  \w     64.00  90.00   1.00    1.00    --   95.80  82.00 -30.00   26
 33  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 34  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-180.00   26
 35  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 36  \w     44.00  70.00   1.00    1.00    --   95.80 -82.00 -60.00   26
 37  \w    108.00 134.00   1.00    1.00    --   95.80  82.00  30.00   26
 38  \w      6.00  78.00   1.00    1.00    --   95.80 -82.00-120.00   72
 39  \w     63.00 107.00   1.00    1.00    --   95.80  82.00 132.91   44
 40  \w      7.00 127.00   1.00    1.00    --   95.80 -82.00  90.00  120
 41  \w    135.00 184.00   1.00    1.00    --   95.80  81.00-108.77   49
 42  \w     63.00  91.00   1.00    1.00    --   95.80  81.00-108.77   28
 43  \w      6.00 128.00   1.00    1.00    --   95.80 -82.00  30.00  122
 44  \w    125.00 185.00   1.00    1.00    --   95.80  63.00  72.56   60
 45  \w    146.00 172.00   1.00    1.00    --   95.80  82.00-120.00   26
 46  \w     68.00 138.00   1.00    1.00    --   95.80  70.00 112.27   70
 47  \w     63.00  97.00   1.00    1.00    --   95.80  82.00   0.00   34
 48  \w    122.00 182.00   1.00    1.00    --   95.80  82.00 132.91   60
 49  \w     66.00  92.00   1.00    1.00    --   95.80  75.00-134.83   26
 50  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-120.00   25
 51  \w     65.00 147.00   1.00    1.00    --   95.80  76.00 -39.79   82
 52  \w    152.00 183.00   1.00    1.00    --   95.80  76.00 -39.79   31
 53  \w     65.00 185.00   1.00    1.00    --   95.80  77.00 -90.00  120
 54  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 55  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 56  \w     70.00  95.00   1.00    1.00    --   95.80  63.00-179.51   25
 57  \w     67.00 128.00   1.00    1.00    --   95.80 -82.00-150.00   61
 58  \w     65.00  95.00   1.00    1.00    --   95.80  77.00   0.00   30
 59  \w    160.00 185.00   1.00    1.00    --   95.80  77.00  90.00   25
 60  \w     65.00 159.00   1.00    1.00    --   95.80  77.00 -30.00   94
 61  \w     65.00 133.00   1.00    1.00    --   95.80  77.00 150.00   68
 62  \w     71.00 178.00   1.00    1.00    --   95.80  61.00  60.00  107
 63  \w     68.00  96.00   1.00    1.00    --   95.80  68.00  35.48   28
 64  \w    136.00 162.00   1.00    1.00    --   95.80  68.00  35.48   26
 65  \w     65.00  90.00   1.00    1.00    --   95.80  78.00 105.83   25
 66  \w    127.00 153.00   1.00    1.00    --   95.80  77.00  90.00   26
 67  \w     67.00  93.00   1.00    1.00    --   95.80  72.00  82.83   26
 68  \w     70.00  95.00   1.00    1.00    --   95.80  63.00  72.56   25
 69  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 70  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 71  \w     34.00 117.00   1.00    1.00    --   95.80 -82.00-180.00   83
 72  \w     67.00 130.00   1.00    1.00    --   95.80  72.00-121.87   63
 73  \w     64.00  90.00   1.00    1.00    --   95.80  81.00-163.44   26
 74  \w     75.00 176.00   1.00    1.00    --   95.80  45.00-120.00  101
 75  \w     65.00 176.00   1.00    1.00    --   95.80  77.00 -11.63  111
 76  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 77  \w     70.00 130.00   1.00    1.00    --   95.80  64.00 -58.82   60
 78  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-120.00   26
 79  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  30.00   25
;
_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      0.0903873000
_diffrn_orient_matrix_UB_12      0.0969805000
_diffrn_orient_matrix_UB_13      -0.0140768000
_diffrn_orient_matrix_UB_21      -0.1301016000
_diffrn_orient_matrix_UB_22      0.0607189000
_diffrn_orient_matrix_UB_23      -0.0181432000
_diffrn_orient_matrix_UB_31      -0.0195456000
_diffrn_orient_matrix_UB_32      0.0442425000
_diffrn_orient_matrix_UB_33      0.0557752000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0601
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            81298
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.460
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.040
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71501
_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    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2330 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.023(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         5514
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0282
_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^)+(0.0453P)^2^+0.5364P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0757
_refine_ls_wR_factor_ref         0.0759
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                5440
_reflns_number_total             5514
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02485g2.cif
_cod_data_source_block           exp_3145
_cod_depositor_comments
'Adding full bibliography for 1569539--1569545.cif.'
_cod_database_code               1569543
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.774
_shelx_estimated_absorpt_t_min   0.732
_reflns_odcompleteness_completeness 99.97
_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)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C34(H34), C33(H33), C32(H32), C31(H31), C30(H30)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C24(H24A,H24B,
 H24C), C23(H23A,H23B,H23C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              62383
_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 1.914
_oxdiff_exptl_absorpt_empirical_full_min 0.560