TfOH-catalyzed cyclization/rearrangement of alkynyl aryl sulfoxides for metal-free synthesis of six- to nine-membered sulfur-containing heterocycles.
Iwanami, Yuto; Tsubouchi, Akira; Noguchi, Keiichi; Saito, Akio; Organic & biomolecular chemistry 24 (2026) 630–635; doi:10.1039/d5ob01829c

data_7161037
_publ_section_title
;
 TfOH-catalyzed cyclization/rearrangement of alkynyl aryl sulfoxides for
 metal-free synthesis of six- to nine-membered sulfur-containing
 heterocycles.
;
_journal_issue                   3
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              630
_journal_page_last               635
_journal_paper_doi               10.1039/d5ob01829c
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C17 H14 O S'
_chemical_formula_sum            'C17 H14 O S'
_chemical_formula_weight         266.34
_chemical_melting_point          390.15
_chemical_name_systematic
(Z)-5-Benzylidene-2,3-dihydrobenzo[b]thiepin-4(5H)-one
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-09-19 deposited with the CCDC.	2025-12-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.413(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7029(4)
_cell_length_b                   9.0406(4)
_cell_length_c                   16.0497(7)
_cell_measurement_reflns_used    18812
_cell_measurement_temperature    263
_cell_measurement_theta_max      68.18
_cell_measurement_theta_min      4.67
_cell_volume                     1374.97(11)
_computing_cell_refinement       'RAPID AUTO'
_computing_data_collection       'RAPID AUTO (Rigaku, 2004)'
_computing_data_reduction        'RAPID AUTO'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      263
_diffrn_detector_area_resol_mean 10.000
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       \w
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0115
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23834
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         68.116
_diffrn_reflns_theta_min         4.907
_diffrn_source                   'rotating anode'
_exptl_absorpt_coefficient_mu    1.982
_exptl_absorpt_correction_T_max  0.452
_exptl_absorpt_correction_T_min  0.272
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'NUMABS (Rigaku, 1999)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.400
_exptl_crystal_size_min          0.400
_refine_diff_density_max         0.418
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2489
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.163
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0482
_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^)+(0.0705P)^2^+0.2795P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1231
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2373
_reflns_number_total             2489
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01829c2.cif
_cod_data_source_block           shelx
_cod_database_code               7161037
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.826
_shelx_estimated_absorpt_t_min   0.790
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00I(H00I,H00J), C00J(H00K,H00L)
2.b Aromatic/amide H refined with riding coordinates:
 C005(H005), C007(H007), C00A(H00A), C00B(H00B), C00C(H00C), C00D(H00D),
 C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H)
;
_shelx_res_checksum              55544
_shelx_hkl_checksum              97506
_olex2_submission_special_instructions 'No special instructions were received'