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_1557616
_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         'C15 H20 O3'
_chemical_formula_sum            'C15 H20 O3'
_chemical_formula_weight         248.31
_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             2019-09-18
_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                82.649(3)
_cell_angle_beta                 76.258(3)
_cell_angle_gamma                68.964(4)
_cell_formula_units_Z            2
_cell_length_a                   7.2165(3)
_cell_length_b                   8.3504(3)
_cell_length_c                   11.3170(4)
_cell_measurement_reflns_used    6955
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.5970
_cell_measurement_theta_min      6.7060
_cell_volume                     617.61(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega   41.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  120.0000 27

  2 omega  -21.00   12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  120.0000 33

  3 omega  -18.00   21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000   38.0000   30.0000 39

  4 omega  -38.00   -3.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  125.0000  120.0000 35

  5 omega  -80.00  -36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000 -180.0000 44

  6 omega   28.00   61.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000   38.0000   30.0000 33

  7 omega  -55.00  -21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       20.0000  160.0000  174.6694 34

  8 omega   -8.00   17.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.0000  100.0000 -137.2139 25

  9 omega    6.00   36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.0000   85.0000   33.6144 30

 10 omega   -2.00   23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   96.0000   69.8149 25

 11 omega    3.00   28.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   87.0000  -94.0549 25

 12 omega    5.00   30.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   90.0000  -58.2564 25

 13 omega   15.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   80.0000   56.7675 25

 14 omega   14.00   39.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   82.0000 -145.9687 25

 15 omega   19.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000  -39.2305 26

 16 omega   20.00   46.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   78.0000  109.6461 26

 17 omega   32.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000    0.0000 77

 18 omega   30.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   66.0000 -114.5049 36

 19 omega   39.00  126.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   57.0000   58.8289 87

 20 omega   41.00   67.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   56.0000 -132.7581 26

 21 omega   85.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   56.0000 -132.7581 26

 22 omega   37.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   74.0000 -105.4160 97

 23 omega   39.00  101.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   73.0000   -6.2651 62

 24 omega  112.00  138.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   70.0000  133.3571 26

 25 omega   41.00   79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   70.0000  133.3571 38

 26 omega   90.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   76.0000  -43.2593 57

 27 omega  106.00  145.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   57.0000  115.9246 39

 28 omega   55.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   57.0000  115.9246 27

 29 omega   45.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   76.0000  -43.2593 26

 30 omega  121.00  151.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       84.0000   53.0000   66.8398 30

 31 omega   84.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       84.0000   53.0000   66.8398 27

 32 omega  126.00  158.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       88.0000   50.0000 -161.5837 32

 33 omega  125.00  157.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       88.0000   55.0000  160.2983 32

 34 omega   66.00   94.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       88.0000   50.0000 -161.5837 28

 35 omega   66.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       88.0000   55.0000  160.2983 27

 36 omega  123.00  157.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       88.0000   71.0000  -27.8578 34

 37 omega   60.00   87.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       88.0000   71.0000  -27.8578 27

 38 omega   63.00  162.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       92.0000   74.0000   37.3235 99

 39 omega  139.00  170.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   68.0000  -31.4462 31

 40 omega   73.00   99.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   68.0000  -31.4462 26

 41 omega  116.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      104.0000   53.0000 -130.2669 57

 42 omega   83.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      104.0000   53.0000 -130.2669 27

 43 omega  114.00  140.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 26

 44 omega   76.00  101.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 25

 45 omega   78.00  164.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 86

 46 omega  118.00  143.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000  -90.0000 25

 47 omega   76.00  144.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 68

 48 omega   77.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 101

 49 omega   76.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 101

 50 omega   76.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 101

 51 omega  130.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 47

 52 omega   77.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 25

 53 omega   42.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -150.0000 67

 54 omega   35.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000  -90.0000 56

 55 omega  108.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 56 omega   80.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 25

 57 omega  144.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   38.0000   30.0000 33

 58 omega  134.00  160.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -90.0000 26

 59 omega   84.00  114.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -90.0000 30

 60 omega   42.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 61

 61 omega  107.00  132.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000 -180.0000 25

 62 omega   76.00  149.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 73

 63 omega   86.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000    0.0000 25

 64 omega   43.00   80.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000 -180.0000 37

 65 omega   84.00  114.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -120.0000 30

 66 omega  135.00  171.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -90.0000 36

 67 omega  153.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 25

 68 omega   85.00  139.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   60.0000 54

 69 omega  143.00  172.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   60.0000 29

 70 omega   86.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  -60.0000 90

 71 omega   62.00  114.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000    0.0000 52

 72 omega  -69.00   22.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -30.0000 91

 73 omega  -22.00   17.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       24.0000  104.0000  -16.5684 39

 74 omega  -43.00  -16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       32.0000  153.0000  -65.6635 27

 75 omega   15.00   46.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   80.0000   56.7675 31

 76 omega   14.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   82.0000 -145.9687 31

 77 omega   19.00   46.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000  121.4124 27

 78 omega   18.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000  -39.2305 27

 79 omega  -20.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000    0.0000 148

 80 omega  -20.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000  -60.0000 148

 81 omega    1.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000   30.0000 97

 82 omega  -20.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000  -90.0000 148

 83 omega  -20.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000  -30.0000 148

 84 omega  -20.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000 -120.0000 148

 85 omega  -20.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000 -180.0000 148

 86 omega  -15.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000 -180.0000 91

 87 omega  -20.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000    0.0000 -150.0000 125
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.2013737000
_diffrn_orient_matrix_UB_12      -0.0344099000
_diffrn_orient_matrix_UB_13      0.0477476000
_diffrn_orient_matrix_UB_21      0.0260389000
_diffrn_orient_matrix_UB_22      -0.0786506000
_diffrn_orient_matrix_UB_23      -0.1213844000
_diffrn_orient_matrix_UB_31      0.1158724000
_diffrn_orient_matrix_UB_32      -0.1782891000
_diffrn_orient_matrix_UB_33      0.0516610000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11512
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        66.587
_diffrn_reflns_theta_max         66.587
_diffrn_reflns_theta_min         4.026
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.736
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68488
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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    1.335
_exptl_crystal_description       block
_exptl_crystal_F_000             268
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.284
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         2182
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0616P)^2^+0.2315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1181
_refine_ls_wR_factor_ref         0.1208
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2021
_reflns_number_total             2182
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00102c2.cif
_cod_data_source_block           zhangye_0917
_cod_depositor_comments
;Adding full bibliography for 1557613--1557618.cif.

 Adding full bibliography for 1557613--1557618.cif.
;
_cod_database_code               1557616
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.59
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C13(H13), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C11(H11A,H11B), C12(H12A,H12B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              71204
_olex2_date_sample_data_collection 2019-09-17
_olex2_submission_special_instructions 'No special instructions were received'