Participation of β-Ketothioamides in N-Heterocyclic Carbene-Catalyzed [3 + 3] Spiroannulation: Asymmetric Synthesis of Functionalized Spiro-piperidinone Derivatives.
Lu, Hong; Tan, Chang-Yin; Zhang, Huan-Xin; Zhang, Jia-Lu; Liu, Jin-Yu; Li, Hong-Yu; Xu, Peng-Fei; The Journal of organic chemistry 83 (2018) 15245–15255; doi:10.1021/acs.joc.8b02520

data_4034774
_publ_section_title
;
 Participation of \b-Ketothioamides in N-Heterocyclic Carbene-Catalyzed [3
 + 3] Spiroannulation: Asymmetric Synthesis of Functionalized
 Spiro-piperidinone Derivatives.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              15245
_journal_page_last               15255
_journal_paper_doi               10.1021/acs.joc.8b02520
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H21 N O2 S'
_chemical_formula_sum            'C26 H21 N O2 S'
_chemical_formula_weight         411.50
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4402(2)
_cell_length_b                   16.5039(6)
_cell_length_c                   19.2685(7)
_cell_measurement_reflns_used    7884
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      66.56
_cell_measurement_theta_min      3.53
_cell_volume                     2048.02(12)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      150.0
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.0681
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            8232
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        66.556
_diffrn_reflns_theta_max         66.556
_diffrn_reflns_theta_min         3.526
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.582
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.3904
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1352 before and 0.0947 after correction. The Ratio of minimum to maximum transmission is 0.5186. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.247
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 1311 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.097(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         3438
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0845P)^2^+0.4565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1278
_refine_ls_wR_factor_ref         0.1289
_reflns_Friedel_coverage         0.673
_reflns_Friedel_fraction_full    0.915
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                3347
_reflns_number_total             3438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02520_si_002.cif
_cod_data_source_block           201712_18c26h21no2s_0m
_cod_database_code               4034774
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
;
_shelx_res_checksum              46270
_shelx_hkl_checksum              67259
_olex2_submission_special_instructions 'No special instructions were received'