Protecting Group-Directed Diastereodivergent Synthesis of Chiral Tetrahydronaphthalene-Fused Spirooxindoles via Bifunctional Tertiary Amine Catalysis.
Wang, Biao; Wang, Xiao-Hui; Huang, Wei; Zhou, Jin; Zhu, Hong-Ping; Peng, Cheng; Han, Bo; The Journal of organic chemistry 84 (2019) 10349–10361; doi:10.1021/acs.joc.9b01501

data_4034057
_publ_section_title
;
 Protecting Group-Directed Diastereodivergent Synthesis of Chiral
 Tetrahydronaphthalene-Fused Spirooxindoles via Bifunctional Tertiary
 Amine Catalysis.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10349
_journal_page_last               10361
_journal_paper_doi               10.1021/acs.joc.9b01501
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H22 Cl N3 O8'
_chemical_formula_sum            'C27 H22 Cl N3 O8'
_chemical_formula_weight         551.92
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-02-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                107.124(8)
_cell_angle_beta                 94.728(8)
_cell_angle_gamma                90.025(7)
_cell_formula_units_Z            2
_cell_length_a                   7.5537(7)
_cell_length_b                   12.8817(11)
_cell_length_c                   13.5102(13)
_cell_measurement_reflns_used    3146
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.0000
_cell_measurement_theta_min      3.8360
_cell_volume                     1251.6(2)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0874
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.834
_diffrn_measurement_details
;
  1 omega  -25.00   24.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -15.1231  -99.0000   60.0000 49

  2 omega  -32.00   40.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -15.1231   57.0000  120.0000 72

  3 omega  -88.00  -63.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -15.1231  178.0000  -90.0000 25

  4 omega  -20.00   23.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -15.1231  -99.0000  150.0000 43

  5 omega  -71.00    0.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -15.1231  -57.0000 -120.0000 71

  6 omega  -79.00   48.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -15.1231    0.0000  -90.0000 127
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0539324000
_diffrn_orient_matrix_UB_12      0.0387066000
_diffrn_orient_matrix_UB_13      0.0319282000
_diffrn_orient_matrix_UB_21      -0.0664396000
_diffrn_orient_matrix_UB_22      -0.0086747000
_diffrn_orient_matrix_UB_23      -0.0420759000
_diffrn_orient_matrix_UB_31      -0.0395051000
_diffrn_orient_matrix_UB_32      -0.0418159000
_diffrn_orient_matrix_UB_33      0.0158247000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.834
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            7683
_diffrn_reflns_point_group_measured_fraction_full 0.539
_diffrn_reflns_point_group_measured_fraction_max 0.446
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.233
_diffrn_reflns_theta_min         3.016
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.211
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64162
_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    1.464
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             572
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.26(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.913
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     708
_refine_ls_number_reflns         7683
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.913
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0465
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0655P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1021
_refine_ls_wR_factor_ref         0.1093
_reflns_Friedel_coverage         0.069
_reflns_Friedel_fraction_full    0.082
_reflns_Friedel_fraction_max     0.058
_reflns_number_gt                5081
_reflns_number_total             7683
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01501_si_003.cif
_cod_data_source_block           161008_s1_unk
_cod_database_code               4034057
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         c12h12n2o3cl1
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.920
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6207
 0.3793
2. 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
3.a Ternary CH refined with riding coordinates:
 C9(H9), C17(H17), C36(H36), C44(H44)
3.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C19(H19A,H19B), C21(H21A,H21B), C43(H43A,H43B), C46(H46A,
 H46B), C48(H48A,H48B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C11(H11), C13(H13), C23(H23), C24(H24), C25(H25),
 C26(H26), C27(H27), C31(H31), C33(H33), C34(H34), C38(H38), C40(H40), C50(H50),
  C51(H51), C52(H52), C53(H53), C54(H54)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C47(H47A,H47B,H47C)
3.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O10(H10)
;
_shelx_res_checksum              13206
_shelx_hkl_checksum              87263
_olex2_submission_special_instructions 'No special instructions were received'