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_7160555
_publ_section_title
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 Photoinitiated thiol-ene mediated functionalisation of 4,5-enoses.
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_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         '2(C46 H51 N O13 S2), H2 O'
_chemical_formula_sum            'C92 H104 N2 O27 S4'
_chemical_formula_weight         1798.01
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-10-08 deposited with the CCDC.	2025-05-13 downloaded from the CCDC.
;
_cell_angle_alpha                81.262(4)
_cell_angle_beta                 85.221(4)
_cell_angle_gamma                81.397(4)
_cell_formula_units_Z            2
_cell_length_a                   10.8947(7)
_cell_length_b                   15.2408(9)
_cell_length_c                   27.3806(16)
_cell_measurement_reflns_used    9888
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.111
_cell_measurement_theta_min      3.175
_cell_volume                     4434.5(5)
_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 (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      100(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device_type  'Bruker APEX Kappa DUO Imus Cuka'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0696
_diffrn_reflns_av_unetI/netI     0.0830
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            90545
_diffrn_reflns_point_group_measured_fraction_full 0.954
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.715
_diffrn_reflns_theta_min         1.635
_diffrn_source_current           0.6
_diffrn_source_power             0.029795999999999996
_diffrn_source_voltage           49.66
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.658
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5532
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS (Krause, 2015) was used for absorption correction.
wR2(int) was 0.1185 before and 0.0854 after correction.
The Ratio of minimum to maximum transmission is 0.7344.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_description       plate
_exptl_crystal_F_000             1900
_exptl_crystal_size_max          0.416
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.654
_refine_diff_density_min         -0.561
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2299
_refine_ls_number_reflns         31569
_refine_ls_number_restraints     273
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1098
_refine_ls_R_factor_gt           0.0884
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1597P)^2^+1.5530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2286
_refine_ls_wR_factor_ref         0.2512
_reflns_Friedel_coverage         0.898
_reflns_Friedel_fraction_full    0.912
_reflns_Friedel_fraction_max     0.875
_reflns_number_gt                24338
_reflns_number_total             31569
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00507h3.cif
_cod_data_source_block           tcd2206
_cod_depositor_comments
'Adding full bibliography for 7160555--7160558.cif.'
_cod_database_code               7160555
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.545
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H45D,H45C} of O2S, All C(H,H) groups, All C(H,H,H,H)
  groups, All N(H) groups, All S(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H1SA,H1SB} of O1S, {H2SA,H2SB} of O2S
2. Restrained distances
 S45D-H45D = S45C-H45C
 1.2 with sigma of 0.01
 S45A-H45A = S45B-H45B
 1.2 with sigma of 0.01
 H2D-H2SA
 2.2 with sigma of 0.01
 C14B-C15E \\sim C14B-C15B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C15B \\sim C15E \\sim C16B \\sim C16E \\sim C17B \\sim C17E \\sim C18B \\sim
C18E \\sim C19B \\sim C19E \\sim C20B \\sim C20E: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Uanis(C15E) = Uanis(C15B)
4. Rigid body (RIGU) restrains
 C15B, C15E, C16B, C16E, C17B, C17E, C18B, C18E, C19B, C19E, C20B, C20E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H14A(0.5) H14B(0.5) H14C(0.5) H14D(0.5) C15B(0.5) C20B(0.5)
 H20B(0.5) C19B(0.5) H19B(0.5) C18B(0.5) H18B(0.5) C17B(0.5) H17B(0.5)
 C16B(0.5) H16B(0.5) C15E(0.5) C20E(0.5) H20E(0.5) C19E(0.5) H19E(0.5)
 C18E(0.5) H18E(0.5) C17E(0.5) H17E(0.5) C16E(0.5) H16E(0.5)
6.a Riding coordinates:
 O1S(H1SA,H1SB), O2S(H2SA,H2SB)
6.b Ternary CH refined with riding coordinates:
 C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C33A(H33A), C34A(H34A),
 C35A(H35A), C36A(H36A), C37A(H37A), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B),
 C6B(H6B), C33B(H33B), C34B(H34B), C35B(H35B), C36B(H36B), C37B(H37B), C2C(H2C),
  C3C(H3C), C4C(H4C), C5C(H5C), C6C(H6C), C33C(H33C), C34C(H34C), C35C(H35C),
 C36C(H36C), C37C(H37C), C2D(H2D), C3D(H3D), C4D(H4D), C5D(H5D), C6D(H6D),
 C33D(H33D), C34D(H34D), C35D(H35D), C36D(H36D), C37D(H37D)
6.c Secondary CH2 refined with riding coordinates:
 C14A(H14E,H14F), C21A(H21C,H21D), C43A(H43C,H43D), C44A(H44C,H44D), C47A(H47C,
 H47D), C14B(H14A,H14B), C14B(H14C,H14D), C21B(H21A,H21B), C43B(H43A,H43B),
 C44B(H44A,H44B), C47B(H47A,H47B), C14C(H14G,H14H), C21C(H21E,H21F), C43C(H43E,
 H43F), C44C(H44E,H44F), C47C(H47E,H47F), C14D(H14I,H14J), C21D(H21G,H21H),
 C43D(H43G,H43H), C44D(H44G,H44H), C47D(H47G,H47H)
6.d Aromatic/amide H refined with riding coordinates:
 N9A(H9A), C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A),
 C26A(H26A), C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A), C49A(H49A),
 C50A(H50A), C51A(H51A), C52A(H52A), C53A(H53A), C58A(H58A), C59A(H59A),
 C60A(H60A), C61A(H61A), C62A(H62A), N9B(H9B), C20B(H20B), C19B(H19B),
 C18B(H18B), C17B(H17B), C16B(H16B), C20E(H20E), C19E(H19E), C18E(H18E),
 C17E(H17E), C16E(H16E), C26B(H26B), C27B(H27B), C28B(H28B), C29B(H29B),
 C30B(H30B), C49B(H49B), C50B(H50B), C51B(H51B), C52B(H52B), C53B(H53B),
 C58B(H58B), C59B(H59B), C60B(H60B), C61B(H61B), C62B(H62B), N9C(H9C),
 C16C(H16C), C17C(H17C), C18C(H18C), C19C(H19C), C20C(H20C), C26C(H26C),
 C27C(H27C), C28C(H28C), C29C(H29C), C30C(H30C), C49C(H49C), C50C(H50C),
 C51C(H51C), C52C(H52C), C53C(H53C), C58C(H58C), C59C(H59C), C60C(H60C),
 C61C(H61C), C62C(H62C), N9D(H9D), C16D(H16D), C17D(H17D), C18D(H18D),
 C19D(H19D), C20D(H20D), C26D(H26D), C27D(H27D), C28D(H28D), C29D(H29D),
 C30D(H30D), C49D(H49D), C50D(H50D), C51D(H51D), C52D(H52D), C53D(H53D),
 C58D(H58D), C59D(H59D), C60D(H60D), C61D(H61D), C62D(H62D)
6.e Fitted hexagon refined as free rotating group:
 C15B(C20B,C19B,C18B,C17B,C16B), C15E(C20E,C19E,C18E,C17E,C16E)
6.f Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C12A(H12D,H12E,H12F), C41A(H41D,H41E,H41F), C8B(H8BA,
 H8BB,H8BC), C12B(H12A,H12B,H12C), C41B(H41A,H41B,H41C), C8C(H8CA,H8CB,H8CC),
 C12C(H12G,H12H,H12I), C41C(H41G,H41H,H41I), C8D(H8DA,H8DB,H8DC), C12D(H12J,
 H12K,H12L), C41D(H41J,H41K,H41L)
;
_shelx_res_checksum              59543
_olex2_exptl_crystal_mounting_method 'mounted in oil on a MiTeGen microloop'
_olex2_submission_original_sample_id HJM124-P2
_olex2_submission_special_instructions 'No special instructions were received'