Highly Enantioselective Sequential Vinylogous Aldol Reaction/Transesterification of Methyl-Substituted Olefinic Butyrolactones with Isatins for the Construction of Chiral Spirocyclic Oxindole-Dihydropyranones
Wang, Zhen-Hua; Zhang, Xia-Yan; Lei, Chuan-Wen; Zhao, Jian-Qiang; you, yong; Yuan, Weicheng; Chemical Communications  (2019) –; doi:10.1039/C9CC04427B

data_7123794
_publ_section_title
;
 Highly Enantioselective Sequential Vinylogous Aldol
 Reaction/Transesterification of Methyl-Substituted Olefinic
 Butyrolactones with Isatins for the Construction of Chiral Spirocyclic
 Oxindole-Dihydropyranones
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC04427B
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H24 Br N O4'
_chemical_formula_sum            'C33 H24 Br N O4'
_chemical_formula_weight         578.44
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-04-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_audit_update_record
;
2018-04-27 deposited with the CCDC.    2019-07-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.307(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2050(2)
_cell_length_b                   9.46603(18)
_cell_length_c                   13.9602(3)
_cell_measurement_reflns_used    5739
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8150
_cell_measurement_theta_min      4.4010
_cell_volume                     1322.39(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega -103.00   -5.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -77.0000 -120.0000 98

  2 omega  -77.00   22.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  104.0000  148.0000 99

  3 omega -108.00  -32.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000  150.0000 76

  4 omega  -52.00   35.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000  -30.0000 87

  5 omega -108.00  -32.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000    0.0000 76

  6 omega  -60.00  -33.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000  -90.0000 27

  7 omega  -49.00   35.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000  -90.0000 84

  8 omega   69.00  110.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   30.0000 41

  9 omega   26.00   89.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -60.0000 63

 10 omega  -34.00   -5.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000 -180.0000 29

 11 omega   12.00   43.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000   90.0000 31

 12 omega    4.00   76.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734 -104.0000   46.0000 72

 13 omega   75.00  101.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -120.0000 26

 14 omega   86.00  115.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  150.0000 29

 15 omega   48.00   87.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 39

 16 omega   38.00   75.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 37

 17 omega   62.00  104.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 42

 18 omega   48.00   87.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 39

 19 omega   41.00   92.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   60.0000 51

 20 omega   44.00   93.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 49

 21 omega   39.00   99.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 60

 22 omega   51.00   84.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 33

 23 omega  112.00  137.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 25

 24 omega   38.00   70.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -150.0000 32

 25 omega   47.00   94.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 47

 26 omega   65.00  170.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  -90.0000 105

 27 omega   43.00   87.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 44

 28 omega   39.00  127.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   60.0000 88

 29 omega   36.00  153.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000   60.0000 117

 30 omega   60.00  113.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -90.0000 53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0033210000
_diffrn_orient_matrix_UB_12      0.0208736000
_diffrn_orient_matrix_UB_13      0.1089512000
_diffrn_orient_matrix_UB_21      0.0417898000
_diffrn_orient_matrix_UB_22      -0.1552052000
_diffrn_orient_matrix_UB_23      0.0202702000
_diffrn_orient_matrix_UB_31      0.1481067000
_diffrn_orient_matrix_UB_32      0.0443245000
_diffrn_orient_matrix_UB_33      0.0197084000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0213
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            9391
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.064
_diffrn_reflns_theta_max         67.064
_diffrn_reflns_theta_min         4.418
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.446
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61035
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.453
_exptl_crystal_description       prism
_exptl_crystal_F_000             592
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/EtOH'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.934
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1965 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         4710
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0374
_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^)+(0.0534P)^2^+0.3875P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0979
_refine_ls_wR_factor_ref         0.1003
_reflns_Friedel_coverage         0.873
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4475
_reflns_number_total             4710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc04427b2.cif
_cod_data_source_block           201804229
_cod_database_code               7123794
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2S1F3Br1
_shelx_estimated_absorpt_t_max   0.742
_shelx_estimated_absorpt_t_min   0.640
_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, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C13(H13A,H13B), C27(H27A,H27B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C11(H11), C12(H12), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20),
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C29(H29), C30(H30), C31(H31),
  C32(H32), C33(H33)
;
_olex2_submission_special_instructions 'No special instructions were received'