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_4518896
_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         'C19 H28 O6'
_chemical_formula_sum            'C19 H28 O6'
_chemical_formula_weight         352.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.1734(15)
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   8.17106(13)
_cell_length_b                   34.8703(6)
_cell_length_c                   9.23924(15)
_cell_measurement_reflns_used    8254
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4250
_cell_measurement_theta_min      4.7730
_cell_volume                     2631.96(8)
_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 0.998
_diffrn_measured_fraction_theta_max 0.969
_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     18.00  45.00   1.00    1.00    --   41.11 -99.00  90.00   27
  2  \w     32.00  81.00   1.00    1.00    --   41.11-125.00  60.00   49
  3  \w     43.00 120.00   1.00    1.00    --  106.95-125.00 -30.00   77
  4  \w     79.00 139.00   1.00    1.00    --  106.95 -77.00   0.00   60
  5  \w    108.00 133.00   1.00    1.00    --  106.95 -30.00 150.00   25
  6  \w     81.00 149.00   1.00    1.00    --  106.95  45.00 150.00   68
  7  \w    101.00 136.00   1.00    1.00    --  106.95 112.00  70.00   35
  8  \w     80.00 164.00   1.00    1.00    --  106.95  30.00  30.00   84
  9  \w    109.00 134.00   1.00    1.00    --  106.95 125.00-150.00   25
 10  \w     42.00  68.00   1.00    1.00    --  106.95 -77.00   0.00   26
 11  \w     39.00  96.00   1.00    1.00    --  106.95 -95.00-180.00   57
 12  \w   -129.00  -4.00   1.00    1.00    --  -41.11   0.00 120.00  125
;
_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      -0.0781545000
_diffrn_orient_matrix_UB_12      0.0393506000
_diffrn_orient_matrix_UB_13      -0.0328234000
_diffrn_orient_matrix_UB_21      0.1715187000
_diffrn_orient_matrix_UB_22      0.0182025000
_diffrn_orient_matrix_UB_23      -0.0056063000
_diffrn_orient_matrix_UB_31      0.0060532000
_diffrn_orient_matrix_UB_32      -0.0085092000
_diffrn_orient_matrix_UB_33      -0.1634472000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0191
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            10571
_diffrn_reflns_point_group_measured_fraction_full 0.752
_diffrn_reflns_point_group_measured_fraction_max 0.717
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.551
_diffrn_reflns_theta_min         2.534
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.809
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80801
_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    1.334
_exptl_crystal_description       block
_exptl_crystal_F_000             1140
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 2296 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     691
_refine_ls_number_reflns         7622
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0346
_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^)+(0.0530P)^2^+0.6700P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0905
_refine_ls_wR_factor_ref         0.0908
_reflns_Friedel_coverage         0.456
_reflns_Friedel_fraction_full    0.496
_reflns_Friedel_fraction_max     0.457
_reflns_number_gt                7556
_reflns_number_total             7622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao1c02054_si_002.cif
_cod_data_source_block           me
_cod_database_code               4518896
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.895
_reflns_odcompleteness_completeness 99.85
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7D(H7D), C7B(H7BA), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C11B(H11C,H11D), C1AA(H1AA,H1AB), C15B(H15C,H15D), C1B(H1BA,H1BB), C4B(H4BA,
 H4BB), C2(H2A,H2B), C14(H14A,H14B), C8(H8A,H8B), C7(H7A,H7B), C9D(H9DA,H9DB),
 C13(H13A,H13B), C2D(H2DA,H2DB), C1(H1A,H1B), C15D(H15E,H15F), C4D(H4DA,H4DB),
 C16D(H16F,H16G), C15(H15A,H15B), C2B(H2BA,H2BB), C11(H11A,H11B), C5B(H5BA,
 H5BB), C16B(H16D,H16E), C1D(H1DA,H1DB), C14D(H14C,H14D), C5D(H5DA,H5DB),
 C18B(H18C,H18D), C19B(H19C,H19D), C18(H18A,H18B), C18D(H18E,H18F), C19D(H19E,
 H19F), C19(H19A,H19B)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C12B(H12D,H12E,H12F), C13B(H13C,
 H13D,H13E), C13D(H13F,H13G,H13H), C12D(H12G,H12H,H12I)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_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 1.497
_oxdiff_exptl_absorpt_empirical_full_min 0.695