Stereoselective Synthesis of trans-Decalin-Based Spirocarbocycles via Photocyclization of 1,2-Diketones
Chen, Sijia; Zhang, Zhongchao; Jiang, Chongguo; Zhao, Chunbo; Luo, Haojie; Huang, Jun; Yang, Zhen; ACS Omega  (2021) –; doi:10.1021/acsomega.1c02054

data_4518895
_publ_section_title
;
 Stereoselective Synthesis of trans-Decalin-Based Spirocarbocycles via
 Photocyclization of 1,2-Diketones
;
_journal_name_full               'ACS Omega'
_journal_paper_doi               10.1021/acsomega.1c02054
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H36 O6'
_chemical_formula_sum            'C24 H36 O6'
_chemical_formula_weight         420.53
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-08-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.08181(13)
_cell_length_b                   10.73068(14)
_cell_length_c                   24.3476(4)
_cell_measurement_reflns_used    8739
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.2910
_cell_measurement_theta_min      3.6210
_cell_volume                     2111.50(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_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   -115.00 -17.00   1.00    1.00    --  -41.11 -38.00-120.00   98
  2  \w   -115.00 -17.00   1.00    1.00    --  -41.11 -38.00 -60.00   98
  3  \w    -69.00  32.00   1.00    1.00    --  -41.11  57.00 150.00  101
  4  \w     23.00  97.00   1.00    1.00    --   41.11-125.00   0.00   74
  5  \w     34.00 133.00   1.00    1.00    --  106.95 -45.00  30.00   99
  6  \w     94.00 178.00   1.00    1.00    --  106.95 125.00 -60.00   84
  7  \w     94.00 178.00   1.00    1.00    --  106.95 125.00 150.00   84
  8  \w     81.00 178.00   1.00    1.00    --  106.95  45.00 -90.00   97
  9  \w     35.00 112.00   1.00    1.00    --  106.95 -61.00-180.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0795058000
_diffrn_orient_matrix_UB_12      -0.1303399000
_diffrn_orient_matrix_UB_13      -0.0029856000
_diffrn_orient_matrix_UB_21      -0.0741248000
_diffrn_orient_matrix_UB_22      0.0188578000
_diffrn_orient_matrix_UB_23      0.0577105000
_diffrn_orient_matrix_UB_31      -0.1565011000
_diffrn_orient_matrix_UB_32      0.0571649000
_diffrn_orient_matrix_UB_33      -0.0258283000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0209
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            9823
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.416
_diffrn_reflns_theta_min         3.631
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.759
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72782
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.230
_refine_diff_density_min         -0.139
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1589 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(5)
_refine_ls_extinction_coef       0.0072(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         4020
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0417P)^2^+0.4438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0731
_refine_ls_wR_factor_ref         0.0734
_reflns_Friedel_coverage         0.679
_reflns_Friedel_fraction_full    0.950
_reflns_Friedel_fraction_max     0.900
_reflns_number_gt                3978
_reflns_number_total             4020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao1c02054_si_003.cif
_cod_data_source_block           csj-cy-2
_cod_original_cell_volume        2111.51(5)
_cod_database_code               4518895
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.908
_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:
 C17(H17), C1(H1A)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C5(H5A,H5B), C18(H18A,H18B), C9(H9A,H9B), C14(H14A,H14B),
 C19(H19A,H19B), C2(H2A,H2B), C20(H20A,H20B), C6(H6A,H6B), C12(H12A,H12B),
 C4(H4A,H4B), C13(H13A,H13B), C3(H3A,H3B), C22(H22A,H22B), C23(H23A,H23B)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_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 1.478
_oxdiff_exptl_absorpt_empirical_full_min 0.658