Facile access to diverse all-carbon quaternary center containing spirobicycles by exploring a tandem Castro–Stephens coupling/acyloxy shift/cyclization/semipinacol rearrangement sequence
Zhang, Ye; Zheng, Tian-Lu; Cheng, Fu; Dai, Kun-Long; Zhang, Kun; Ma, Ai-Jun; Zhang, Fu-Min; Zhang, Xiao-Ming; Wang, Shao-Hua; Tu, Yong-Qiang; Chemical Science 11 (2020) 3878–3884; doi:10.1039/D0SC00102C

data_1557613
_publ_section_title
;
 Facile access to diverse all-carbon quaternary center containing
 spirobicycles by exploring a tandem Castro--Stephens coupling/acyloxy
 shift/cyclization/semipinacol rearrangement sequence
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              3878
_journal_page_last               3884
_journal_paper_doi               10.1039/D0SC00102C
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C22 H28 O5 S'
_chemical_formula_sum            'C22 H28 O5 S'
_chemical_formula_weight         404.50
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-29 deposited with the CCDC.	2020-03-11 downloaded from the CCDC.
;
_cell_angle_alpha                92.571(3)
_cell_angle_beta                 96.250(4)
_cell_angle_gamma                97.449(4)
_cell_formula_units_Z            2
_cell_length_a                   7.3975(3)
_cell_length_b                   10.7485(5)
_cell_length_c                   13.1441(5)
_cell_measurement_reflns_used    5801
_cell_measurement_temperature    292.1(3)
_cell_measurement_theta_max      69.8890
_cell_measurement_theta_min      6.7770
_cell_volume                     1028.29(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292.1(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_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     44.00 116.00   1.00    1.50    --  108.00-111.00 150.00   72
  2  \w     41.00  95.00   1.00    1.50    --  108.00 -63.00 150.00   54
  3  \w     43.00  72.00   1.00    1.00    --   64.00  42.00 130.49   29
  4  \w     67.00  98.00   1.00    1.50    --   84.00  46.00 157.56   31
  5  \w     86.00 112.00   1.00    1.50    --  108.00  63.00 150.00   26
  6  \w    112.00 168.00   1.00    1.50    --  108.00  77.00 120.00   56
  7  \w     98.00 125.00   1.00    1.00    --   60.00  76.00  40.65   27
  8  \w     83.00 114.00   1.00    1.50    --  104.00  60.00  -4.43   31
  9  \w    113.00 169.00   1.00    1.50    --  108.00  77.00 -30.00   56
 10  \w    116.00 177.00   1.00    1.50    --  108.00  77.00 -90.00   61
 11  \w    102.00 151.00   1.00    1.50    --  108.00 178.00   0.00   49
 12  \w     79.00 176.00   1.00    1.50    --  108.00  77.00   0.00   97
 13  \w     84.00 130.00   1.00    1.00    --   64.00  66.00-124.42   46
 14  \w     87.00 112.00   1.00    1.50    --  108.00  63.00-150.00   25
 15  \w     78.00 168.00   1.00    1.50    --  108.00  77.00-150.00   90
 16  \w     83.00 110.00   1.00    1.50    --  108.00  38.00   0.00   27
 17  \w     78.00 160.00   1.00    1.50    --  108.00  77.00 -60.00   82
 18  \w     87.00 112.00   1.00    1.50    --  108.00  63.00  60.00   25
 19  \w     79.00 177.00   1.00    1.50    --  108.00  77.00  30.00   98
 20  \w     86.00 112.00   1.00    1.50    --  108.00  63.00 -60.00   26
 21  \w     78.00 104.00   1.00    1.50    --  108.00  77.00 -30.00   26
 22  \w     78.00 113.00   1.00    1.50    --  108.00  77.00 -90.00   35
 23  \w     79.00 160.00   1.00    1.50    --  108.00  77.00-120.00   81
 24  \w     81.00 177.00   1.00    1.50    --  108.00  77.00-180.00   96
 25  \w     59.00  92.00   1.00    1.50    --   88.00  75.00-163.19   33
 26  \w     54.00 103.00   1.00    1.00    --   80.00  72.00 -92.70   49
 27  \w     51.00 106.00   1.00    1.00    --   72.00  55.00  -3.17   55
 28  \w     71.00 100.00   1.00    1.50    --   92.00  54.00  56.73   29
 29  \w     78.00 154.00   1.00    1.50    --  108.00  77.00  60.00   76
 30  \w     78.00 176.00   1.00    1.50    --  108.00  77.00 150.00   98
 31  \w     79.00 107.00   1.00    1.50    --  108.00  77.00 120.00   28
 32  \w     80.00 166.00   1.00    1.50    --  108.00  77.00  90.00   86
 33  \w     67.00  93.00   1.00    1.50    --   88.00  51.00 129.95   26
 34  \w     48.00  75.00   1.00    1.00    --   68.00  55.00 138.24   27
 35  \w     49.00 140.00   1.00    1.00    --   72.00  66.00 164.20   91
 36  \w     41.00  68.00   1.00    1.00    --    0.00  19.00 -30.00   27
 37  \w     17.00  44.00   1.00    1.00    --   48.00  78.00-115.08   27
 38  \w     41.00  79.00   1.00    1.00    --   64.00  66.00-124.42   38
 39  \w     48.00 113.00   1.00    1.00    --   76.00  77.00 -72.18   65
 40  \w     47.00 133.00   1.00    1.00    --   68.00  63.00  23.94   86
 41  \w     43.00 130.00   1.00    1.00    --   72.00  75.00-110.92   87
 42  \w     45.00  70.00   1.00    1.00    --    0.00  38.00-180.00   25
 43  \w     24.00  50.00   1.00    1.00    --   54.00  77.00-150.00   26
 44  \w     37.00  62.00   1.00    1.00    --   60.00  67.00-174.60   25
 45  \w     28.00  74.00   1.00    1.00    --   56.00  73.00-131.03   46
 46  \w     20.00  45.00   1.00    1.00    --   52.00  81.00 -38.20   25
 47  \w     24.00  50.00   1.00    1.00    --   54.00  77.00   0.00   26
 48  \w     31.00  66.00   1.00    1.00    --   60.00  76.00  40.65   35
 49  \w     27.00  66.00   1.00    1.00    --   54.00  77.00  60.00   39
 50  \w     38.00  64.00   1.00    1.00    --   60.00  62.00 118.01   26
 51  \w     15.00  43.00   1.00    1.00    --   48.00  82.00 153.27   28
 52  \w      9.00  34.00   1.00    1.00    --   44.00  85.00  96.32   25
 53  \w      5.00  30.00   1.00    1.00    --   40.00  85.00  65.41   25
 54  \w      2.00  40.00   1.00    1.00    --    0.00  19.00 -30.00   38
 55  \w     43.00 138.00   1.00    1.50    --  108.00 -77.00 -30.00   95
 56  \w     53.00  89.00   1.00    1.50    --  108.00-111.00-180.00   36
 57  \w     28.00  87.00   1.00    1.00    --   54.00-125.00 -90.00   59
 58  \w     36.00 116.00   1.00    1.50    --  108.00-111.00 -30.00   80
 59  \w      6.00  85.00   1.00    1.00    --   54.00 -99.00  60.00   79
 60  \w    -14.00  74.00   1.00    1.00    --   54.00 -57.00 -90.00   88
 61  \w    -20.00  30.00   1.00    1.00    --    0.00  38.00-180.00   50
 62  \w      7.00  33.00   1.00    1.00    --   44.00  89.00 -77.24   26
 63  \w     25.00  51.00   1.00    1.00    --   54.00  77.00 -60.00   26
 64  \w    -28.00  -3.00   1.00    1.00    --    0.00  19.00 -30.00   25
 65  \w    -24.00   4.00   1.00    1.00    --   24.00 111.00  68.59   28
 66  \w    -19.00  43.00   1.00    1.00    --    0.00 -19.00 120.00   62
 67  \w     -8.00  72.00   1.00    1.00    --   54.00 -57.00 120.00   80
 68  \w    -24.00   1.00   1.00    1.00    --   28.00 117.00-130.18   25
 69  \w    -62.00 -33.00   1.00    1.00    --    0.00 -19.00 120.00   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0698395000
_diffrn_orient_matrix_UB_12      0.1028010000
_diffrn_orient_matrix_UB_13      -0.0658448000
_diffrn_orient_matrix_UB_21      0.0336692000
_diffrn_orient_matrix_UB_22      -0.0739443000
_diffrn_orient_matrix_UB_23      -0.0977321000
_diffrn_orient_matrix_UB_31      -0.1967211000
_diffrn_orient_matrix_UB_32      -0.0702378000
_diffrn_orient_matrix_UB_33      -0.0080497000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            14982
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.589
_diffrn_reflns_theta_max         66.589
_diffrn_reflns_theta_min         4.156
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.651
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48684
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.306
_exptl_crystal_description       plate
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.304
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         3632
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0428
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0634P)^2^+0.2953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1223
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3088
_reflns_number_total             3632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00102c2.cif
_cod_data_source_block           zhangy_0626
_cod_depositor_comments
;Adding full bibliography for 1557613--1557618.cif.

 Adding full bibliography for 1557613--1557618.cif.
;
_cod_database_code               1557613
_shelx_shelxl_version_number     2018/3
_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, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C18(H18), C20(H20), C21(H21)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_shelx_res_checksum              11369
_olex2_date_sample_data_collection 2019-06-27
_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 1.618
_oxdiff_exptl_absorpt_empirical_full_min 0.443