Chemodivergent synthesis of <i>cis</i>-4-hydroxyprolines from diastereomerically enriched epoxides.
DaSilva, Clement; Mauk, Grace; Forshee, Lucas; Pope, Oliver; Doherty, Mathilde; Ongbongan, Max; Lutz, Nicholas; Kamanya, Zemirah; Bhatt, Kara Chris; Braham, Andrew; Kubek, Miranda; Hawthorne, Summer; Campillo-Alvarado, Gonzalo; Bhattacharjee, Avik; Bowring, Miriam A.; O'Brien, Robert V; Organic & biomolecular chemistry 23 (2025) 4616–4621; doi:10.1039/d4ob01815j

data_7160348
_publ_section_title
;
 Chemodivergent synthesis of <i>cis</i>-4-hydroxyprolines from
 diastereomerically enriched epoxides.
;
_journal_issue                   19
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4616
_journal_page_last               4621
_journal_paper_doi               10.1039/d4ob01815j
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C14 H19 N O5 S'
_chemical_formula_sum            'C14 H19 N O5 S'
_chemical_formula_weight         313.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-12
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-09-19 deposited with the CCDC.	2025-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4970(17)
_cell_length_b                   20.881(3)
_cell_length_c                   6.4271(12)
_cell_measurement_reflns_used    1767
_cell_measurement_temperature    99.97(16)
_cell_measurement_theta_max      20.9200
_cell_measurement_theta_min      2.0200
_cell_volume                     1542.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.118a 64-bit (release 27-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -64.00  78.00   0.50   48.00    --   20.00  54.00  60.00  284
  2  \w    -59.00 -34.00   0.50   48.00    --   20.00  54.00 150.00   50
  3  \w    -11.00  15.00   0.50   48.00    --   20.00  54.00 150.00   52
  4  \w     84.00 109.00   0.50   48.00    --   20.00  54.00 150.00   50
  5  \w    -60.00 -16.00   0.50   48.00    --   20.00  54.00-150.00   88
  6  \w     20.00  45.00   0.50   48.00    --   20.00  54.00-150.00   50
  7  \w    -54.00  84.00   0.50   48.00    --   20.00  54.00 -90.00  276
  8  \w     37.00  62.00   0.50   48.00    --   20.00  54.00  30.00   50
  9  \w     -3.00 105.00   0.50   48.00    --   20.00  54.00 -60.00  216
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0263035000
_diffrn_orient_matrix_UB_12      0.0247845000
_diffrn_orient_matrix_UB_13      -0.0591654000
_diffrn_orient_matrix_UB_21      -0.0305165000
_diffrn_orient_matrix_UB_22      -0.0232045000
_diffrn_orient_matrix_UB_23      -0.0590484000
_diffrn_orient_matrix_UB_31      -0.0467027000
_diffrn_orient_matrix_UB_32      0.0012947000
_diffrn_orient_matrix_UB_33      0.0720600000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0928
_diffrn_reflns_av_unetI/netI     0.1095
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            10443
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        24.990
_diffrn_reflns_theta_max         24.990
_diffrn_reflns_theta_min         2.635
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.230
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.980
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (Rigaku Oxford Diffraction, 2024)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       needle
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.988
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 551 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     194
_refine_ls_number_reflns         2707
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.983
_refine_ls_R_factor_all          0.1056
_refine_ls_R_factor_gt           0.0577
_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^)+(0.0387P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1030
_refine_ls_wR_factor_ref         0.1127
_reflns_Friedel_coverage         0.818
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                1730
_reflns_number_total             2707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01815j2.cif
_cod_data_source_block           rvo_04112024_needle_autored
_cod_depositor_comments
'Adding full bibliography for 7160347--7160350.cif.'
_cod_original_cell_volume        1543.0(4)
_cod_database_code               7160348
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.805
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3A), C1(H1A)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C12(H12), C13(H13), C9(H9), C10(H10)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C6(H6A,H6B,H6C), C14(H14A,H14B,H14C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              80430
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.008
_oxdiff_exptl_absorpt_empirical_full_min 0.545