Base-promoted cascade haloamination/β-elimination of alkenyl thianthrenium salts: access to (<i>Z</i>)-β-chloroenamines.
Lv, Qing-Long; Fan, Yue; Qi, Yuanbing; Lu, Yuzhe; Xue, Yinjiang; Shi, Ao-Tong; Xia, Hongqiang; Li, Dianjun; Organic & biomolecular chemistry 24 (2026) 2225–2229; doi:10.1039/d6ob00027d

data_7161018
_publ_section_title
;
 Base-promoted cascade haloamination/&#x3b2;-elimination of alkenyl
 thianthrenium salts: access to (<i>Z</i>)-&#x3b2;-chloroenamines.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2225
_journal_page_last               2229
_journal_paper_doi               10.1039/d6ob00027d
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C27 H30 Cl N O2 S'
_chemical_formula_sum            'C27 H30 Cl N O2 S'
_chemical_formula_weight         468.03
_chemical_name_systematic
(Z)-N-(2-([1,1'-biphenyl]-4-yl)-2-chlorovinyl)-N-hexyl-4-methylbenzenesulfonamide
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-09-19
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-09-22 deposited with the CCDC.	2026-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.007(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.5758(3)
_cell_length_b                   20.3604(10)
_cell_length_c                   22.2066(12)
_cell_measurement_reflns_used    1672
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      16.608
_cell_measurement_theta_min      2.201
_cell_volume                     2514.9(2)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2025/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 'Bruker PHOTON-II area detector'
_diffrn_detector_area_resol_mean 7.4
_diffrn_detector_type            'CMOS-PHOTONII area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker PHOTON-II area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1229
_diffrn_reflns_av_unetI/netI     0.0752
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            31299
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.499
_diffrn_reflns_theta_max         24.499
_diffrn_reflns_theta_min         1.358
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.258
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1099 before and 0.0659 after correction.
The Ratio of minimum to maximum transmission is 0.8969.
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    1.236
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.061
_refine_ls_extinction_coef       0.016(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     540
_refine_ls_number_reflns         4196
_refine_ls_number_restraints     909
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.2045
_refine_ls_R_factor_gt           0.0940
_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^)+(0.1165P)^2^+5.9385P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2332
_refine_ls_wR_factor_ref         0.3325
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1676
_reflns_number_total             4196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ob00027d2.cif
_cod_data_source_block           lql
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7161018.cif.
;
_cod_database_code               7161018
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.967
_exptl_crystal_mounting_method
;
 Crystals were removed from the crystallisation vial and immediately coated
 with PDMS (polydimethylsiloxane/Dimethicone, CAS: 9006-65-9 on a glass slide.
 A suitable single crystal was selected and mounted on a glass fiber using
 vacuum silicone grease as adhesive. The glass fiber with single crystal was
 mounted on copper pin with solid paraffin. Operator: DJ_Tokyo.
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C11-C10 = C15-C10 = C15-C14 = C14-C13 = C13-C12 = C12-C11 = C17-C16 = C21-C16
 = C21-C20 = C20-C19 = C19-C18 = C18-C17
 1.395 with sigma of 0.01
3. Restrained planarity
 C10, C11, C12, C13, C14, C15, C9, C16
 with sigma of 0.01
 C16, C17, C18, C19, C20, C21, C13
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
S1 \\sim O1 \\sim O2 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6
\\sim C7 \\sim O1A \\sim O2A \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A
\\sim C6A \\sim C7A: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C23A \\sim C24A
\\sim C25A \\sim C26A \\sim C27A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C9 \\sim Cl1 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim
C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim Cl1A \\sim C10A
\\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A \\sim C17A
\\sim C18A \\sim C19A \\sim C20A \\sim C21A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
5. Same fragment restrains
{S1, O1A, O2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{S1, O1, O2, C1, C2, C3, C4, C5, C6, C7}
{C9, Cl1A, C10A, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A,
C21A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C9, Cl1, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21}
{C22, C23A, C24A, C25A, C26A, C27A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C22, C23, C24, C25, C26, C27}
6. Others
 Sof(O1A)=Sof(O2A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=1-
 FVAR(1)
 Sof(O1)=Sof(O2)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=
 Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(1)
 Sof(H22C)=Sof(H22D)=Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24C)=
 Sof(H24D)=Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(2)
 Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=
 Sof(H27B)=Sof(H27C)=FVAR(2)
 Sof(Cl1A)=Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(C17A)=Sof(H17A)=
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=1-FVAR(3)
 Sof(Cl1)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=
 Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C22(H22C,H22D), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C26(H26A,H26B), C23A(H23C,H23D), C24A(H24C,H24D), C25A(H25C,H25D),
 C26A(H26C,H26D)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C11(H11), C12(H12), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C11A(H11A),
 C12A(H12A), C14A(H14A), C15A(H15A), C17A(H17A), C18A(H18A), C19A(H19A),
 C20A(H20A), C21A(H21A), C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A)
7.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C27(H27A,H27B,H27C), C7A(H7AA,H7AB,H7AC), C27A(H27D,H27E,H27F)
;
_shelx_res_checksum              79665
_olex2_submission_special_instructions 'No special instructions were received'