Ag(I)-catalyzed asymmetric (2+4) annulation reaction of 5-alkenyl thiazolones: synthesis of enantioenriched spiro[cyclohexenamines-thiazolones].
Choudhary, Kavita; Deshpande, Akanksha Santosh; Singh, Vinod K.; Chemical communications (Cambridge, England) 60 (2024) 9062–9065; doi:10.1039/d4cc02957g

data_7133451
_publ_section_title
;
 Ag(I)-catalyzed asymmetric (2+4) annulation reaction of 5-alkenyl
 thiazolones: synthesis of enantioenriched
 spiro[cyclohexenamines-thiazolones].
;
_journal_issue                   68
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9062
_journal_page_last               9065
_journal_paper_doi               10.1039/d4cc02957g
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C27 H17.35 N3 O S, C27 H18 N3 O S, 2[C4H8O2]'
_chemical_formula_sum            'C62 H51.35 N6 O6 S2'
_chemical_formula_weight         1040.56
_chemical_name_systematic        KC1247
_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     dual
_audit_creation_date             2024-05-30
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.11.24 svn.r209d9fb2 for OlexSys, GUI svn.r6869)
;
_audit_update_record
;
2024-05-30 deposited with the CCDC.	2024-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                95.1110(10)
_cell_angle_beta                 94.0180(10)
_cell_angle_gamma                111.2480(10)
_cell_formula_units_Z            1
_cell_length_a                   10.2217(3)
_cell_length_b                   11.1542(3)
_cell_length_c                   13.1904(4)
_cell_measurement_reflns_used    9942
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      28.29
_cell_measurement_theta_min      2.32
_cell_volume                     1387.58(7)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            22504
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.340
_diffrn_reflns_theta_min         2.791
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.153
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6854
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1387 before and 0.0521 after correction.
The Ratio of minimum to maximum transmission is 0.9191.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.245
_exptl_crystal_description       needle
_exptl_crystal_F_000             545
_exptl_crystal_preparation       'SOLVENT EVAPORATION'
_exptl_crystal_recrystallization_method 'SOLVENT EVAPORATION'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.484
_refine_diff_density_min         -0.639
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 5130 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     634
_refine_ls_number_reflns         13649
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0640
_refine_ls_R_factor_gt           0.0576
_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^)+(0.0725P)^2^+0.6252P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1424
_refine_ls_wR_factor_ref         0.1486
_reflns_Friedel_coverage         0.980
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                12329
_reflns_number_total             13649
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02957g2.cif
_cod_data_source_block           27octb_0m
_cod_depositor_comments          'Adding full bibliography for 7133451.cif.'
_cod_database_code               7133451
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.970
_olex2_refinement_description
;
1. Restrained distances
 C18-C28 \\sim C18-C22
 with sigma of 0.02
 C28-C29 \\sim C22-C23
 with sigma of 0.02
 C28-C33 \\sim C22-C27
 with sigma of 0.02
 C29-C30 \\sim C23-C24
 with sigma of 0.02
 C33-C32 \\sim C27-C26
 with sigma of 0.02
 C30-C31 \\sim C24-C25
 with sigma of 0.02
 C32-C31 \\sim C26-C25
 with sigma of 0.02
 C18-C29 \\sim C18-C23
 with sigma of 0.04
 C18-C33 \\sim C18-C27
 with sigma of 0.04
 C28-C30 \\sim C22-C24
 with sigma of 0.04
 C28-C32 \\sim C22-C26
 with sigma of 0.04
 C29-C33 \\sim C23-C27
 with sigma of 0.04
 C29-C31 \\sim C23-C25
 with sigma of 0.04
 C33-C31 \\sim C27-C25
 with sigma of 0.04
 C30-C32 \\sim C24-C26
 with sigma of 0.04
 C13-C4 \\sim C13-C10
 with sigma of 0.02
 C4-C5 \\sim C10-C11
 with sigma of 0.02
 C4-C3 \\sim C10-C9
 with sigma of 0.02
 C2-C1 \\sim C8-C7
 with sigma of 0.02
 C2-C3 \\sim C8-C9
 with sigma of 0.02
 C1-C6 \\sim C7-C12
 with sigma of 0.02
 C5-C6 \\sim C11-C12
 with sigma of 0.02
 C13-C5 \\sim C13-C11
 with sigma of 0.04
 C13-C3 \\sim C13-C9
 with sigma of 0.04
 C4-C2 \\sim C10-C8
 with sigma of 0.04
 C4-C6 \\sim C10-C12
 with sigma of 0.04
 C2-C6 \\sim C8-C12
 with sigma of 0.04
 C1-C5 \\sim C7-C11
 with sigma of 0.04
 C1-C3 \\sim C7-C9
 with sigma of 0.04
 C5-C3 \\sim C11-C9
 with sigma of 0.04
 C19-C18 \\sim C19-C18A
 with sigma of 0.02
 C18-C17 \\sim C18A-C17
 with sigma of 0.02
 C18-C28 \\sim C18A-C28
 with sigma of 0.02
 C18-C22 \\sim C18A-C22
 with sigma of 0.02
 C16-C17 \\sim C16-C17A
 with sigma of 0.02
 C18-C17 \\sim C18-C17A
 with sigma of 0.02
 C17-C21 \\sim C17A-C21A
 with sigma of 0.02
 C17-C18A \\sim C17A-C18A
 with sigma of 0.02
 C21-N6 \\sim C21A-N6A
 with sigma of 0.02
 C16-C21 \\sim C16-C21A
 with sigma of 0.04
 C18-C21 \\sim C18-C21A
 with sigma of 0.04
 C17-N6 \\sim C17A-N6A
 with sigma of 0.04
 C21-C18A \\sim C21A-C18A
 with sigma of 0.04
 C72-C67 \\sim C72A-C67A
 with sigma of 0.02
 C72-C71 \\sim C72A-C71A
 with sigma of 0.02
 C67-C68 \\sim C67A-C68A
 with sigma of 0.02
 C68-C69 \\sim C68A-C69A
 with sigma of 0.02
 C69-C70 \\sim C69A-C70A
 with sigma of 0.02
 C71-C70 \\sim C71A-C70A
 with sigma of 0.02
 C72-C68 \\sim C72A-C68A
 with sigma of 0.04
 C72-C70 \\sim C72A-C70A
 with sigma of 0.04
 C67-C69 \\sim C67A-C69A
 with sigma of 0.04
 C67-C71 \\sim C67A-C71A
 with sigma of 0.04
 C68-C70 \\sim C68A-C70A
 with sigma of 0.04
 C69-C71 \\sim C69A-C71A
 with sigma of 0.04
 C60-C59 \\sim C60A-C59A
 with sigma of 0.02
 C59-C58 \\sim C59A-C58A
 with sigma of 0.02
 C56-C57 \\sim C56A-C57A
 with sigma of 0.02
 C58-C57 \\sim C58A-C57A
 with sigma of 0.02
 C60-C43 \\sim C60A-C43
 with sigma of 0.04
 C60-C56 \\sim C60A-C56A
 with sigma of 0.04
 C60-C58 \\sim C60A-C58A
 with sigma of 0.04
 C43-C56 \\sim C43-C56A
 with sigma of 0.04
 C59-C57 \\sim C59A-C57A
 with sigma of 0.04
 C56-C58 \\sim C56A-C58A
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
Uanis(C17) = Uanis(C21) = Uanis(N6)
Uanis(C31) = Uanis(C32) = Uanis(C30) = Uanis(C56) = Uanis(C57) = Uanis(C58)
Uanis(C58) = Uanis(C57) = Uanis(C56) = Uanis(C30) = Uanis(C31) = Uanis(C32)
Uanis(C26) = Uanis(C24) = Uanis(C25) = Uanis(C27) = Uanis(C23) = Uanis(C22) =
Uanis(C33) = Uanis(C32) = Uanis(C31) = Uanis(C30) = Uanis(C29) = Uanis(C28)
Uanis(C55) = Uanis(C60) = Uanis(C59)
Uanis(C55) = Uanis(C60) = Uanis(C59) = Uanis(C58) = Uanis(C57) = Uanis(C56)
Uanis(C71A) = Uanis(C71)
Uanis(C12) = Uanis(C7) = Uanis(C8) = Uanis(C10) = Uanis(C2) = Uanis(C1) =
Uanis(C6) = Uanis(C3) = Uanis(C9) = Uanis(C11) = Uanis(C5) = Uanis(C4)
3. Rigid body (RIGU) restrains
 C57, C58, C56, C30, C31, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: C60(0.45) H60(0.45) H43(0.45) C59(0.45) H59(0.45) C56(0.45)
 H56(0.45) C4(0.45) C2(0.45) H2(0.45) C1(0.45) H1(0.45) C5(0.45) H5(0.45)
 C58(0.55) H58(0.55) C6(0.45) H6(0.45) C57(0.45) H57(0.45) C3(0.45) H3(0.45)
 C18(0.45) C17(0.45) C21(0.45) N6(0.45) C28(0.45) C29(0.45) H29(0.45) C33(0.45)
 H33(0.45) C30(0.45) H30(0.45) C32(0.45) H32(0.45) C31(0.45) H31(0.45)
 C22(0.55) C27(0.55) H27(0.55) C26(0.55) H26(0.55) C25(0.55) H25(0.55)
 C24(0.55) H24(0.55) C23(0.55) H23(0.55) C72(0.45) H72(0.45) C67(0.45)
 C68(0.45) H68(0.45) C69(0.45) H69(0.45) C71(0.45) H71(0.45) C70(0.45)
 H70(0.45) C10(0.55) C8(0.55) H8(0.55) C7(0.55) H7(0.55) C11(0.55) H11(0.55)
 C12(0.55) H12(0.55) C9(0.55) H9(0.55) C18A(0.55) C17A(0.55) C21A(0.55)
 N6A(0.55) C72A(0.55) H72A(0.55) C67A(0.55) C68A(0.55) H68A(0.55) C69A(0.55)
 H69A(0.55) C71A(0.55) H71A(0.55) C70A(0.55) H70A(0.55) C60A(0.55) C59A(0.55)
 H59A(0.55) C56A(0.55) C58A(0.45) H58A(0.45) C57A(0.55) H57A(0.55)
5.a Ternary CH refined with riding coordinates:
 C43(H43), C20(H20)
5.b Aromatic/amide H refined with riding coordinates:
 C51(H51), C60(H60), C39(H39), C37(H37), C35(H35), C38(H38), C50(H50),
 C52(H52), C42(H42), C36(H36), C54(H54), C53(H53), C59(H59), C56(H56), C2(H2),
 C1(H1), C5(H5), C58(H58), C6(H6), C57(H57), C3(H3), C29(H29), C33(H33),
 C30(H30), C32(H32), C31(H31), C27(H27), C26(H26), C25(H25), C24(H24), C23(H23),
  C72(H72), C68(H68), C69(H69), C71(H71), C70(H70), C8(H8), C7(H7), C11(H11),
 C12(H12), C9(H9), C72A(H72A), C68A(H68A), C69A(H69A), C71A(H71A), C70A(H70A),
 C59A(H59A), C58A(H58A), C57A(H57A)
5.c X=CH2 refined with riding coordinates:
 N2(H2A,H2B), N5(H5A,H5B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              55738
_shelx_hkl_checksum              8233
_shelx_fab_checksum              34004
_olex2_exptl_crystal_mounting_method 'SILICON RING'
_olex2_submission_original_sample_id KC1247
_olex2_submission_special_instructions 'No special instructions were received'