Isothiourea-catalysed enantioselective synthesis of phosphonate-functionalised β-lactones
Platt, Ffion M.; Wang, Yihong; Cordes, David B.; McKay, Aidan P.; Slawin, Alexandra M. Z.; Panchal, Heena; Smith, Andrew D.; Chemical Science 16 (2025) 6828–6836; doi:10.1039/D5SC00322A

data_1574062
_publ_section_title
;
 Isothiourea-catalysed enantioselective synthesis of
 phosphonate-functionalised \b-lactones
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              6828
_journal_page_last               6836
_journal_paper_doi               10.1039/D5SC00322A
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H17 O5 P S'
_chemical_formula_sum            'C19 H17 O5 P S'
_chemical_formula_weight         388.35
_chemical_name_systematic
'dimethyl ((2R,3R)-3-(benzo[b]thiophen-3-yl)-4-oxo-2-phenyloxetan-2-yl)phosphonate'
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-12
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-14 deposited with the CCDC.	2025-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.666(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.3633(5)
_cell_length_b                   7.8457(3)
_cell_length_c                   12.0190(6)
_cell_measurement_reflns_used    14427
_cell_measurement_temperature    125
_cell_measurement_theta_max      74.0400
_cell_measurement_theta_min      3.9080
_cell_volume                     914.35(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      125
_diffrn_detector                 'hybrid photon counting detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris PILATUS P200K'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.969
_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    -89.00  89.00   0.50    1.56    --    0.00  32.00  74.00  356
  2  \w   -186.00  -8.00   0.50    6.23    --  -97.10  32.00  74.00  356
  3  \w    -84.00  94.00   0.50    1.56    --    5.00  32.00  74.00  356
  4  \w   -121.00  57.00   0.50    1.56    --  -32.00  44.00 -24.61  356
  5  \w   -129.00  49.00   0.50    1.56    --  -40.00  53.00 118.08  356
  6  \w   -129.00  49.00   0.50    1.56    --  -40.00  55.00-133.01  356
  7  \w   -129.00  49.00   0.50    1.56    --  -40.00  53.00 118.08  356
  8  \w   -133.00  45.00   0.50    1.56    --  -44.00  55.00 -40.61  356
  9  \w   -137.00  41.00   0.50    1.56    --  -48.00  55.00-161.17  356
 10  \w   -141.00  37.00   0.50    6.23    --  -52.00  55.00  54.06  356
 11  \w   -141.00  37.00   0.50    6.23    --  -52.00  55.00 -51.74  356
 12  \w   -145.00  33.00   0.50    6.23    --  -56.00  54.00-125.08  356
 13  \w   -145.00  33.00   0.50    6.23    --  -56.00  55.00  91.96  356
 14  \w   -145.00  33.00   0.50    6.23    --  -56.00  55.00 132.59  356
 15  \w   -131.00  29.00   0.50    6.23    --  -60.00  55.00  17.55  320
 16  \w     -2.00  25.00   0.50    6.23    --  -64.00  55.00 -54.26   54
 17  \w    -34.00  25.00   0.50    6.23    --  -64.00  54.00-121.86  118
 18  \w   -119.00 -50.00   0.50    6.23    --  -64.00  54.00-121.86  138
 19  \w     -8.00  20.00   0.50    6.23    --  -68.00  53.00  72.49   56
 20  \w     -5.00  21.00   0.50    6.23    --  -68.00  55.00 -12.07   52
 21  \w     -8.00  20.00   0.50    6.23    --  -68.00  55.00-154.64   56
 22  \w    -11.00  21.00   0.50    6.23    --  -68.00  52.00 -76.59   64
 23  \w    -15.00  14.00   0.50    6.23    --  -72.00  55.00 148.21   58
 24  \w   -118.00 -92.00   0.50    6.23    --  -72.00  55.00 148.21   52
 25  \w    -13.00  13.00   0.50    6.23    --  -76.00  55.00 118.57   52
 26  \w    -22.00   9.00   0.50    6.23    --  -80.00  55.00 179.76   62
 27  \w    -25.00   8.00   0.50    6.23    --  -80.00  51.00  70.75   66
 28  \w   -160.00 -56.00   0.50    6.23    --  -80.00  55.00 179.76  208
 29  \w   -172.00   4.00   0.50    6.23    --  -84.00  49.00 -92.42  352
 30  \w   -110.00 -46.00   0.50    6.23    --  -88.00  55.00   2.95  128
 31  \w   -172.00-146.00   0.50    6.23    --  -88.00  55.00   2.95   52
 32  \w    -42.00  -1.00   0.50    6.23    --  -88.00  55.00   2.95   82
 33  \w    -33.00  -4.00   0.50    6.23    --  -92.00  55.00  76.94   58
 34  \w   -118.00 -79.00   0.50    6.23    --  -92.00  55.00  76.94   78
 35  \w   -181.00-123.00   0.50    6.23    --  -92.00  55.00  76.94  116
 36  \w   -132.00  -8.00   0.50    6.23    --  -96.00  54.00 -40.49  248
 37  \w   -169.00 -11.00   0.50    6.23    --  -96.00  54.00-167.29  316
 38  \w   -170.00 -12.00   0.50    6.23    --  -97.10  46.00  60.00  316
 39  \w   -180.00  -8.00   0.50    6.23    --  -97.10  55.00 -53.80  344
 40  \w   -124.00 -11.00   0.50    6.23    --  -97.10  46.00-150.00  226
 41  \w    -36.00  -9.00   0.50    6.23    --  -97.10  53.00  -7.06   54
 42  \w    -55.00 -11.00   0.50    6.23    --  -97.10  53.00-103.96   88
 43  \w   -117.00  -8.00   0.50    6.23    --  -97.10  46.00  30.00  218
 44  \w    -99.00 -64.00   0.50    6.23    --  -97.10  53.00-103.96   70
 45  \w   -184.00-158.00   0.50    6.23    --  -97.10  53.00-103.96   52
 46  \w    -73.00  -8.00   0.50    6.23    --  -97.10  55.00 122.97  130
 47  \w   -168.00 -10.00   0.50    6.23    --  -97.10  53.00 139.12  316
 48  \w   -101.00 -76.00   0.50    6.23    --  -97.10  55.00 122.97   50
;
_diffrn_measurement_device       'AFC11: Quarter \c 4 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200K'
_diffrn_measurement_method       'shutterless scans'
_diffrn_measurement_specimen_support Loop
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0930665000
_diffrn_orient_matrix_UB_12      0.0517180000
_diffrn_orient_matrix_UB_13      -0.0698819000
_diffrn_orient_matrix_UB_21      -0.0261282000
_diffrn_orient_matrix_UB_22      0.1893952000
_diffrn_orient_matrix_UB_23      0.0184971000
_diffrn_orient_matrix_UB_31      0.1261061000
_diffrn_orient_matrix_UB_32      0.0009882000
_diffrn_orient_matrix_UB_33      0.1163983000
_diffrn_radiation_monochromator  'Rigaku Osmic Confocal Optical System'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1138
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            33520
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.194
_diffrn_reflns_theta_min         3.931
_diffrn_source                   'Rotating Anode'
_diffrn_source_type              'Rigaku MM-007HF'
_exptl_absorpt_coefficient_mu    2.644
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13720
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       needle
_exptl_crystal_F_000             404
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Methyl tert-butyl ether/hexane'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.495
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1166 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(2)
_refine_ls_extinction_coef       0.008(2)
_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   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3660
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0621
_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^)+(0.0989P)^2^+0.3599P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1613
_refine_ls_wR_factor_ref         0.1855
_reflns_Friedel_coverage         0.838
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                3089
_reflns_number_total             3660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00322a2.cif
_cod_data_source_block           55
_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 1574060--1574062.cif.
;
_cod_original_sg_symbol_H-M      P21
_cod_database_code               1574062
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.677
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C18(H18), C19(H19),
 C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              24703