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_4034056
_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         'C28 H32 Cl N3 O10 Si, 0.5(C4 H8 O2)'
_chemical_formula_sum            'C30 H36 Cl N3 O11 Si'
_chemical_formula_weight         678.15
_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   geom
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.8238(10)
_cell_length_b                   16.1894(12)
_cell_length_c                   31.377(2)
_cell_measurement_reflns_used    9957
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      20.774
_cell_measurement_theta_min      3.183
_cell_volume                     7022.1(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0982
_diffrn_reflns_av_unetI/netI     0.1084
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            109326
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.585
_diffrn_reflns_theta_min         2.988
_exptl_absorpt_coefficient_mu    0.202
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6589
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0677 before and 0.0594 after correction. The Ratio of minimum to maximum transmission is 0.8837. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             2848
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.217
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.309
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2558 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.886
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     896
_refine_ls_number_reflns         16190
_refine_ls_number_restraints     618
_refine_ls_restrained_S_all      0.918
_refine_ls_R_factor_all          0.1613
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0648P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0985
_refine_ls_wR_factor_ref         0.1229
_reflns_Friedel_coverage         0.830
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                7025
_reflns_number_total             16190
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01501_si_002.cif
_cod_data_source_block           222
_cod_depositor_comments
;

2025-10-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C60 H72 Cl2 N6 O22 Si2'
_cod_original_formula_weight         1356.31
_cod_original_formula_moiety         '2(C28 H32 Cl N3 O10 Si), C4 H8 O2'
_cod_original_formula_units_Z            4
_cod_original_cell_volume        7022.2(9)
_cod_database_code               4034056
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.942
_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. Restrained distances
 C55-N5
 1.44 with sigma of 0.02
 C6-C1A
 1.4 with sigma of 0.02
 Si2-C59
 1.8 with sigma of 0.02
 O14-N5 \\sim N5-O13
 with sigma of 0.02
 C58-Si2 \\sim Si2-C58A
 with sigma of 0.02
3. Rigid bond restraints
 O5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 Si2, C59, C60, C58, C59A, C58A, C60A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=1-FVAR(1)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=FVAR(1)
 Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C58A)=Sof(H58D)=Sof(H58E)=
 Sof(H58F)=Sof(C60A)=Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(2)
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C8(H8), C12(H12), C50(H50), C46(H46)
7.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C49(H49A,H49B), C2(H2A,H2B), C52(H52A,H52B), C6(H6A,H6B),
 C6A(H6AA,H6AB)
7.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C16(H16), C22(H22), C14(H14), C43(H43), C42(H42), C21(H21),
 C45(H45), C54(H54), C56(H56)
7.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C31(H31A,H31B,H31C), C27(H27A,H27B,H27C), C35(H35A,H35B,
 H35C), C33(H33A,H33B,H33C), C59(H59A,H59B,H59C), C34(H34A,H34B,H34C), C60(H60A,
 H60B,H60C), C58(H58A,H58B,H58C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C28(H28A,H28B,H28C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C53(H53A,H53B,H53C),
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC), C59A(H59D,H59E,H59F), C58A(H58D,H58E,
 H58F), C60A(H60D,H60E,H60F)
;
_shelx_res_checksum              7221
_shelx_hkl_checksum              5820
_olex2_submission_special_instructions 'No special instructions were received'