Asymmetric synthesis of highly functionalized spirothiazolidinone tetrahydroquinolines via a squaramide-catalyzed cascade reaction.
Song, Yong-Xing; Du, Da-Ming; Organic & biomolecular chemistry 16 (2018) 9390–9401; doi:10.1039/c8ob02731e

data_7156586
_publ_section_title
;
 Asymmetric synthesis of highly functionalized spirothiazolidinone
 tetrahydroquinolines via a squaramide-catalyzed cascade reaction.
;
_journal_issue                   48
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9390
_journal_page_last               9401
_journal_paper_doi               10.1039/c8ob02731e
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H32 N2 O7 S3'
_chemical_formula_sum            'C36 H32 N2 O7 S3'
_chemical_formula_weight         700.81
_chemical_melting_point          474.5(15)
_chemical_name_systematic
'Ethyl (2R,3R,4R)-4-(2-(4-methoxyphenyl)-2-oxoethyl)-4'-oxo-3'-phenyl-2'-thioxo-1-tosyl-1,4-dihydro-2H-spiro[quinoline-3,5'-thiazolidine]-2-carboxylate'
_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             2018-11-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-20 deposited with the CCDC.
2018-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.433(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6715(11)
_cell_length_b                   18.093(2)
_cell_length_c                   22.594(3)
_cell_measurement_reflns_used    9508
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      21.32
_cell_measurement_theta_min      2.39
_cell_volume                     3486.2(7)
_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)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_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  0.0336
_diffrn_reflns_av_unetI/netI     0.0421
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            33508
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        24.815
_diffrn_reflns_theta_max         24.815
_diffrn_reflns_theta_min         1.833
_exptl_absorpt_coefficient_mu    0.264
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6903
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2014/5'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_description       block
_exptl_crystal_F_000             1464
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Petroleum ether-Ethyl acetate'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.194
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 3762 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     926
_refine_ls_number_reflns         11918
_refine_ls_number_restraints     254
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0380
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0401P)^2^+0.3121P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0789
_refine_ls_wR_factor_ref         0.0869
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                9410
_reflns_number_total             11918
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob02731e2.cif
_cod_data_source_block           mo_20180822_ddm_syx_411_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value '473-476' was changed to '474.5(15)'
- the average value was taken and precision was estimated.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 7156586.cif.
;
_cod_original_cell_volume        3486.2(8)
_cod_database_code               7156586
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.949
_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
 C60A-C59A = C60-C59 = C61A-C60A = C61-C60 = C61A-C56A = C61-C56 = C57-C56 =
 C57A-C56A = C58A-C57A = C58-C57 = C59A-C58A = C59-C58
 1.39 with sigma of 0.02
 C60A-C59A
 1.39 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C61A \\sim C60A
\\sim C59A \\sim C58A \\sim C57A \\sim C56A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.01
Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C61A) \\sim Ueq,
Uanis(C60A) \\sim Ueq, Uanis(C59A) \\sim Ueq, Uanis(C58A) \\sim Ueq,
Uanis(C57A) \\sim Ueq, Uanis(C56A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(C61A)=Sof(H61A)=Sof(C60A)=Sof(H60A)=Sof(C59A)=Sof(H59A)=Sof(C58A)=
 Sof(H58A)=Sof(C57A)=Sof(H57A)=Sof(C56A)=1-FVAR(1)
 Sof(C56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=
 Sof(H60)=Sof(C61)=Sof(H61)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C26(H26), C46(H46), C62(H62)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C28(H28A,H28B), C45(H45A,H45B), C64(H64A,H64B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14), C15(H15),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C31(H31), C32(H32), C34(H34),
  C35(H35), C39(H39), C40(H40), C42(H42), C43(H43), C48(H48), C49(H49),
 C50(H50), C51(H51), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C67(H67),
  C68(H68), C70(H70), C71(H71), C61A(H61A), C60A(H60A), C59A(H59A), C58A(H58A),
 C57A(H57A)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C65(H65A,H65B,H65C), C72(H72A,H72B,H72C)
;
_olex2_submission_special_instructions 'No special instructions were received'