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_1557614
_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 H22 O3'
_chemical_formula_sum            'C15 H22 O3'
_chemical_formula_weight         250.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-10-18
_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                90
_cell_angle_beta                 101.329(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.6688(3)
_cell_length_b                   22.4305(6)
_cell_length_c                   15.4747(5)
_cell_measurement_reflns_used    5177
_cell_measurement_temperature    292.89(12)
_cell_measurement_theta_max      69.4980
_cell_measurement_theta_min      6.1850
_cell_volume                     2610.02(15)
_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      292.89(12)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.959
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_details
;
  1 omega  -60.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  125.0000 -120.0000 45

  2 omega  -69.00  -44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000  120.0000 25

  3 omega  -86.00  -40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000  -60.0000 46

  4 omega   -7.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000   60.0000 47

  5 omega   23.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  -30.0000 68

  6 omega  -14.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -77.0000   90.0000 91

  7 omega   36.00   63.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -12.0000  -30.0000 27

  8 omega   39.00   93.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000  120.0000 54

  9 omega   35.00   69.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  120.0000 34

 10 omega   37.00   99.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   30.0000 62

 11 omega   76.00  102.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000 -120.0000 26

 12 omega  102.00  176.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000    0.0000 74

 13 omega   76.00  178.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -12.0000  -30.0000 102

 14 omega   47.00   79.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -120.0000 32

 15 omega   69.00   97.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   25.0000   60.0000 28

 16 omega   35.00   61.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -91.0000 -120.0000 26

 17 omega   59.00   93.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000   60.0000 34

 18 omega   45.00  126.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000  -60.0000 81

 19 omega  -49.00  -23.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  111.0000   60.0000 26

 20 omega   30.00   56.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000   57.0000 -120.0000 26

 21 omega  -16.00   27.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -38.0000 -180.0000 43

 22 omega   51.00   81.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  -90.0000 30

 23 omega  150.00  176.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -60.0000 26

 24 omega   53.00   79.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  -30.0000 26

 25 omega   45.00   71.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -120.0000 26

 26 omega  110.00  136.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -60.0000 26

 27 omega   90.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -120.0000 25

 28 omega   59.00  113.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 54
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1221208000
_diffrn_orient_matrix_UB_12      -0.0452613000
_diffrn_orient_matrix_UB_13      0.0337416000
_diffrn_orient_matrix_UB_21      0.1404157000
_diffrn_orient_matrix_UB_22      -0.0082940000
_diffrn_orient_matrix_UB_23      0.0851597000
_diffrn_orient_matrix_UB_31      -0.0855389000
_diffrn_orient_matrix_UB_32      0.0509989000
_diffrn_orient_matrix_UB_33      0.0438501000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0372
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.959
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12604
_diffrn_reflns_point_group_measured_fraction_full 0.959
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        66.595
_diffrn_reflns_theta_max         66.595
_diffrn_reflns_theta_min         3.517
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72852
_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    1.274
_exptl_crystal_description       block
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.279
_refine_diff_density_min         -0.175
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         4422
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0456
_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^)+(0.0703P)^2^+0.4835P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1221
_refine_ls_wR_factor_ref         0.1371
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3722
_reflns_number_total             4422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00102c2.cif
_cod_data_source_block           zhangye_1015
_cod_depositor_comments
;

 Adding full bibliography for 1557613--1557618.cif.

2022-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        2610.00(14)
_cod_original_formula_moiety     '2(C15 H22 O3)'
_cod_original_formula_sum        'C30 H44 O6'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     500.65
_cod_database_code               1557614
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 95.86
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C22(H22), C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C15(H15A,H15B), C19(H19A,H19B), C21(H21A,H21B),
 C23(H23A,H23B), C24(H24A,H24B), C26(H26A,H26B), C30(H30A,H30B), C32(H32A,H32B),
  C11(H11A,H11B), C14(H14A,H14B), C25(H25A,H25B), C27(H27A,H27B), C28(H28A,
 H28B), C31(H31A,H31B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B),
 C36(H36A,H36B)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3), O6(H6)
;
_shelx_res_checksum              66820
_olex2_date_sample_data_collection 2019-10-16
_olex2_submission_special_instructions 'No special instructions were received'