Photoinitiated thiol-ene mediated functionalisation of 4,5-enoses.
Prieto-Castañeda, Alejandro; Martin, Harlei; Manna, Tapasi; Beswick, Laura; McLean, Joshua T.; Pongener, Imlirenla; González, Inés Rabadán; Twamley, Brendan; Miller, Gavin J.; Scanlan, Eoin M.; Organic & biomolecular chemistry 23 (2025) 5332–5338; doi:10.1039/d5ob00507h

data_7160556
_publ_section_title
;
 Photoinitiated thiol-ene mediated functionalisation of 4,5-enoses.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5332
_journal_page_last               5338
_journal_paper_doi               10.1039/d5ob00507h
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H18 O8 S2'
_chemical_formula_sum            'C13 H18 O8 S2'
_chemical_formula_weight         366.39
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-05-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-08 deposited with the CCDC.	2025-05-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.130(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.1441(5)
_cell_length_b                   8.1239(4)
_cell_length_c                   11.0985(5)
_cell_measurement_reflns_used    3743
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.507
_cell_measurement_theta_min      4.849
_cell_volume                     822.32(7)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2016)'
_computing_data_collection       'APEX 4 (Bruker, 2021)'
_computing_data_reduction        'SAINT v8.37A (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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            APEX2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX2 Kappa Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       APEX2
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0610
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            12870
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.347
_diffrn_reflns_theta_min         3.993
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.6
_diffrn_source_power             0.029778
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           49.63
_exptl_absorpt_coefficient_mu    3.296
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5710
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS (Krause, 2015) was used for absorption correction.
wR2(int) was 0.1078 before and 0.0750 after correction.
The Ratio of minimum to maximum transmission is 0.7580.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.480
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.358
_exptl_crystal_size_mid          0.034
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.180
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 1130 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         3072
_refine_ls_number_restraints     475
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0935P)^2^+0.1507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1413
_refine_ls_wR_factor_ref         0.1476
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                2725
_reflns_number_total             3072
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00507h3.cif
_cod_data_source_block           tcd2284
_cod_depositor_comments
'Adding full bibliography for 7160555--7160558.cif.'
_cod_database_code               7160556
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.902
_shelx_estimated_absorpt_t_min   0.385
_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
 O8-H8
 1 with sigma of 0.01
 C2B-C3 \\sim C2A-C3
 with sigma of 0.02
 S2B-C2B \\sim S2A-C2A
 with sigma of 0.02
 S2B-C9B \\sim S2A-C9A
 with sigma of 0.02
 C9B-C8B \\sim C8A-C9A
 with sigma of 0.02
 S1B-C8B \\sim S1A-C8A
 with sigma of 0.02
 S1B-C1B \\sim S1A-C1A
 with sigma of 0.02
 C1A-C2A \\sim C2B-C1B
 with sigma of 0.02
 C1A-C11A \\sim C1B-C11B
 with sigma of 0.02
 O1A-C1A \\sim O1B-C1B
 with sigma of 0.02
 O1B-C5 \\sim O1A-C5
 with sigma of 0.02
 O2B-C11B \\sim O2A-C11A
 with sigma of 0.02
 O3B-C11B \\sim O3A-C11A
 with sigma of 0.02
 O2A-C14A \\sim O2B-C14B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1A \\sim O1A \\sim C1A \\sim S2A \\sim O2A \\sim C2A \\sim O3A \\sim C8A \\sim
C9A \\sim C11A \\sim C14A \\sim S1B \\sim O1B \\sim C1B \\sim S2B \\sim O2B
\\sim C2B \\sim O3B \\sim C8B \\sim C9B \\sim C11B \\sim C14B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 S1A, O1A, C1A, S2A, O2A, C2A, O3A, C8A, C9A, C11A, C14A, S1B, O1B, C1B, S2B,
 O2B, C2B, O3B, C8B, C9B, C11B, C14B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H3B)=Sof(H5B)=Sof(S1B)=Sof(O1B)=Sof(C1B)=Sof(S2B)=Sof(O2B)=Sof(C2B)=
 Sof(H2B)=Sof(O3B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=
 Sof(C11B)=Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(1)
 Sof(H3A)=Sof(H5A)=Sof(S1A)=Sof(O1A)=Sof(C1A)=Sof(S2A)=Sof(O2A)=Sof(C2A)=
 Sof(H2A)=Sof(O3A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(C11A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C3(H3B), C3(H3A), C4(H4), C5(H5B), C5(H5A), C2A(H2A), C2B(H2B)
6.b Secondary CH2 refined with riding coordinates:
 C8A(H8AA,H8AB), C9A(H9AA,H9AB), C8B(H8BA,H8BB), C9B(H9BA,H9BB)
6.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C14A(H14A,H14B,H14C), C14B(H14D,
 H14E,H14F)
;
_shelx_res_checksum              72538
_olex2_exptl_crystal_mounting_method 'mounted in oil on a MiTiGen microloop '
_olex2_submission_original_sample_id IRG_APC_039
_olex2_submission_special_instructions 'No special instructions were received'