Asymmetric [3 + 2] Cycloaddition Reaction of Isatin-Derived MBH Carbonates with 3-Methyleneoxindoles: Enantioselective Synthesis of 3,3'-Cyclopentenyldispirooxindoles Incorporating Two Adjacent Quaternary Spirostereocenters.
Chen, Yu; Cui, Bao-Dong; Wang, Yi; Han, Wen-Yong; Wan, Nan-Wei; Bai, Mei; Yuan, Wei-Cheng; Chen, Yong-Zheng; The Journal of organic chemistry 83 (2018) 10465–10475; doi:10.1021/acs.joc.8b01506

data_4035070
_publ_section_title
;
 Asymmetric [3 + 2] Cycloaddition Reaction of Isatin-Derived MBH
 Carbonates with 3-Methyleneoxindoles: Enantioselective Synthesis of
 3,3'-Cyclopentenyldispirooxindoles Incorporating Two Adjacent Quaternary
 Spirostereocenters.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10465
_journal_page_last               10475
_journal_paper_doi               10.1021/acs.joc.8b01506
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H24 N2 O5'
_chemical_formula_sum            'C30 H24 N2 O5'
_chemical_formula_weight         492.51
_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   geom
_audit_creation_date             2017-10-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9113(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.98962(8)
_cell_length_b                   9.43940(12)
_cell_length_c                   14.40897(12)
_cell_measurement_reflns_used    15912
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.3360
_cell_measurement_theta_min      4.9030
_cell_volume                     1218.21(2)
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.993
_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   -113.00 -13.00   1.00    1.00    --  -41.11 -57.00  90.00  100
  2  \w   -113.00 -13.00   1.00    1.00    --  -41.11 -57.00 150.00  100
  3  \w   -117.00  -9.00   1.00    1.00    --  -41.11 -77.00  90.00  108
  4  \w    -65.00  33.00   1.00    1.00    --  -41.11  37.00 120.00   98
  5  \w    -65.00  33.00   1.00    1.00    --  -41.11  37.00  30.00   98
  6  \w   -116.00 -17.00   1.00    1.00    --  -41.11 -37.00  90.00   99
  7  \w     23.00  97.00   1.00    1.00    --   41.11-125.00-180.00   74
  8  \w     17.00 116.00   1.00    1.00    --   41.11  37.00-180.00   99
  9  \w     17.00 116.00   1.00    1.00    --   41.11  37.00 120.00   99
 10  \w     74.00 178.00   1.00    1.73    --  106.95  77.00-180.00  104
 11  \w     81.00 178.00   1.00    1.73    --  106.95  45.00-180.00   97
 12  \w     78.00 178.00   1.00    1.73    --  106.95  61.00 120.00  100
 13  \w     81.00 178.00   1.00    1.73    --  106.95  45.00-150.00   97
 14  \w     78.00 178.00   1.00    1.73    --  106.95  61.00 150.00  100
 15  \w     74.00 178.00   1.00    1.73    --  106.95  77.00-150.00  104
 16  \w     24.00 109.00   1.00    1.73    --  106.95 -94.00-150.00   85
 17  \w     78.00 178.00   1.00    1.73    --  106.95  61.00-150.00  100
 18  \w     74.00 178.00   1.00    1.73    --  106.95  77.00  90.00  104
 19  \w     78.00 178.00   1.00    1.73    --  106.95  61.00-180.00  100
 20  \w     81.00 178.00   1.00    1.73    --  106.95  45.00  90.00   97
 21  \w     74.00 178.00   1.00    1.73    --  106.95  77.00 150.00  104
 22  \w     24.00 109.00   1.00    1.73    --  106.95 -94.00 -60.00   85
 23  \w     34.00 121.00   1.00    1.73    --  106.95-125.00-120.00   87
 24  \w     74.00 178.00   1.00    1.73    --  106.95  77.00 120.00  104
 25  \w     81.00 178.00   1.00    1.73    --  106.95  45.00 150.00   97
 26  \w     81.00 178.00   1.00    1.73    --  106.95  45.00-120.00   97
 27  \w     74.00 178.00   1.00    1.73    --  106.95  77.00  60.00  104
 28  \w     81.00 178.00   1.00    1.73    --  106.95  45.00 120.00   97
 29  \w     78.00 178.00   1.00    1.73    --  106.95  61.00  90.00  100
 30  \w     94.00 178.00   1.00    1.73    --  106.95 125.00  90.00   84
 31  \w     84.00 110.00   1.00    1.73    --  106.95  30.00 150.00   26
;
_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      0.0937510000
_diffrn_orient_matrix_UB_12      0.0347895000
_diffrn_orient_matrix_UB_13      -0.0817428000
_diffrn_orient_matrix_UB_21      0.1441360000
_diffrn_orient_matrix_UB_22      -0.0185685000
_diffrn_orient_matrix_UB_23      0.0646726000
_diffrn_orient_matrix_UB_31      0.0036198000
_diffrn_orient_matrix_UB_32      -0.1584200000
_diffrn_orient_matrix_UB_33      -0.0254113000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21830
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.663
_diffrn_reflns_theta_min         4.938
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.752
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56378
_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    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             516
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1943 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         4617
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0438
_refine_ls_R_factor_gt           0.0429
_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^)+(0.0845P)^2^+0.1566P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1152
_refine_ls_wR_factor_ref         0.1161
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.906
_reflns_Friedel_fraction_max     0.877
_reflns_number_gt                4541
_reflns_number_total             4617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01506_si_001.cif
_cod_data_source_block           exp_872
_cod_database_code               4035070
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C9(H9), C15(H15), C18(H18), C3(H3), C16(H16), C24(H24), C11(H11),
 C12(H12), C23(H23), C22(H22), C17(H17), C10(H10), C25(H25)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C26(H26A,H26B,H26C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.541
_oxdiff_exptl_absorpt_empirical_full_min 0.628