Understanding divergent substrate stereoselectivity in the isothiourea-catalysed conjugate addition of cyclic α-substituted β-ketoesters to α,β-unsaturated aryl esters.
Yuan, Ding; Goodfellow, Alister S.; Kasten, Kevin; Duan, Zhuan; Kang, Tengfei; Cordes, David B.; McKay, Aidan P.; Bühl, Michael; Boyce, Gregory R.; Smith, Andrew D.; Chemical science 14 (2023) 14146–14156; doi:10.1039/d3sc05470e

data_1570360
_publ_section_title
;
 Understanding divergent substrate stereoselectivity in the
 isothiourea-catalysed conjugate addition of cyclic &#x3b1;-substituted
 &#x3b2;-ketoesters to &#x3b1;,&#x3b2;-unsaturated aryl esters.
;
_journal_issue                   48
_journal_name_full               'Chemical science'
_journal_page_first              14146
_journal_page_last               14156
_journal_paper_doi               10.1039/d3sc05470e
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H22 F3 N O4'
_chemical_formula_sum            'C23 H22 F3 N O4'
_chemical_formula_weight         433.41
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-03 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.9425(2)
_cell_length_b                   18.8834(3)
_cell_length_c                   22.2420(4)
_cell_measurement_reflns_used    29952
_cell_measurement_temperature    173
_cell_measurement_theta_max      66.3980
_cell_measurement_theta_min      3.0570
_cell_volume                     4175.90(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.82a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.82a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.82a (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      173
_diffrn_detector                 'hybrid photon counting detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris PILATUS P100K'
_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    -23.00  47.00   1.00    1.00    --    0.00 -82.00  60.00   70
  2  \w    -20.00  35.00   1.00    1.00    --    0.00  77.00 -90.00   55
  3  \w    -20.00  35.00   1.00    1.00    --    0.00  77.00 -30.00   55
  4  \w    -83.00 -12.00   1.00    1.00    --    0.00 -19.00  60.00   71
  5  \w    -83.00 -12.00   1.00    1.00    --    0.00 -19.00   0.00   71
  6  \w    -15.00  35.00   1.00    1.00    --    5.00  77.00 120.00   50
  7  \w    -15.00  35.00   1.00    1.00    --    5.00  77.00  60.00   50
  8  \w    -15.00  35.00   1.00    1.00    --    5.00  77.00-150.00   50
  9  \w    -78.00  -7.00   1.00    1.00    --    5.00 -19.00 -60.00   71
 10  \w     17.00  94.00   1.00    1.00    --    5.00  19.00  60.00   77
 11  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00-120.00  116
 12  \w    -70.00  32.00   1.00    1.00    --  -57.40  57.00 -60.00  102
 13  \w   -141.00 -88.00   1.00    1.00    --  -57.40 -77.00  30.00   53
 14  \w   -141.00 -88.00   1.00    1.00    --  -57.40 -77.00  90.00   53
 15  \w   -141.00 -53.00   1.00    1.00    --  -57.40 -37.00 150.00   88
 16  \w   -141.00 -69.00   1.00    1.00    --  -57.40 -19.00  30.00   72
 17  \w   -141.00 -69.00   1.00    1.00    --  -57.40 -19.00-120.00   72
 18  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00-150.00  116
 19  \w   -101.00   6.00   1.00    1.00    --  -83.30  77.00 -60.00  107
 20  \w    -97.00 -20.00   1.00    1.00    -- -109.20  82.00 -57.77   77
 21  \w    -97.00 -20.00   1.00    1.00    -- -109.20  82.00  56.07   77
 22  \w   -124.00 -20.00   1.00    1.00    -- -109.20  63.00  11.81  104
 23  \w   -193.00-107.00   1.00    1.00    -- -109.20 -35.00  93.67   86
 24  \w   -193.00 -71.00   1.00    1.00    -- -109.20 -71.00-123.46  122
 25  \w   -112.00 -20.00   1.00    1.00    -- -109.20  37.00  90.00   92
 26  \w   -193.00 -71.00   1.00    1.00    -- -109.20 -70.00 155.55  122
 27  \w   -193.00 -76.00   1.00    1.00    -- -109.20 -60.00 167.74  117
 28  \w   -193.00 -72.00   1.00    1.00    -- -109.20 -69.00  71.26  121
 29  \w   -193.00 -96.00   1.00    1.00    -- -109.20 -45.00-153.60   97
 30  \w    -97.00 -20.00   1.00    1.00    -- -109.20  82.00-155.28   77
 31  \w   -193.00 -69.00   1.00    1.00    -- -109.20 -73.00-171.60  124
 32  \w   -193.00 -69.00   1.00    1.00    -- -109.20 -73.00-138.27  124
 33  \w   -193.00 -88.00   1.00    1.00    -- -109.20 -77.00  50.84  105
 34  \w    -87.00 -21.00   1.00    1.00    -- -109.20  82.00  30.13   66
 35  \w   -191.00-100.00   1.00    1.00    -- -109.20 -77.00 136.95   91
 36  \w   -124.00 -72.00   1.00    1.00    -- -109.20 -71.00 -98.64   52
 37  \w    -58.00 -30.00   1.00    1.00    -- -109.20  81.00-137.55   28
 38  \w   -154.00-128.00   1.00    1.00    -- -109.20 -71.00 -98.64   26
 39  \w   -125.00 -95.00   1.00    1.00    -- -109.20 -48.00  57.55   30
 40  \w   -120.00 -70.00   1.00    1.00    -- -109.20 -72.00-107.92   50
 41  \w   -155.00-115.00   1.00    1.00    -- -109.20 -27.00  67.72   40
 42  \w   -155.00-130.00   1.00    1.00    -- -109.20 -25.00 173.05   25
 43  \w    -99.00 -73.00   1.00    1.00    -- -109.20 -71.00-117.31   26
 44  \w   -187.00-135.00   1.00    1.00    -- -109.20 -35.00  19.24   52
 45  \w    -97.00 -44.00   1.00    1.00    -- -109.20  82.00 -15.94   53
 46  \w   -162.00-136.00   1.00    1.00    -- -109.20 -48.00  57.55   26
 47  \w   -176.00-146.00   1.00    1.00    -- -109.20 -33.00 105.01   30
 48  \w   -138.00-109.00   1.00    1.00    -- -109.20 -33.00 105.01   29
 49  \w   -160.00-132.00   1.00    1.00    -- -109.20 -71.00-117.31   28
 50  \w   -121.00 -86.00   1.00    1.00    -- -109.20 -52.00 -61.02   35
 51  \w   -117.00 -91.00   1.00    1.00    -- -109.20 -51.00  89.07   26
 52  \w   -132.00 -73.00   1.00    1.00    -- -109.20 -72.00-155.25   59
 53  \w    -97.00 -59.00   1.00    1.00    -- -109.20  82.00-110.87   38
 54  \w   -191.00-150.00   1.00    1.00    -- -109.20 -63.00 119.79   41
 55  \w   -175.00-149.00   1.00    1.00    -- -109.20 -51.00  89.07   26
 56  \w   -112.00 -68.00   1.00    1.00    -- -109.20  61.00 148.51   44
 57  \w   -102.00 -76.00   1.00    1.00    -- -109.20 -63.00 119.79   26
 58  \w   -102.00 -70.00   1.00    1.00    -- -109.20 -72.00-132.35   32
 59  \w   -161.00-136.00   1.00    1.00    -- -109.20 -19.00 -30.00   25
 60  \w    -73.00 -39.00   1.00    1.00    -- -109.20  82.00  18.83   34
 61  \w    -65.00 -39.00   1.00    1.00    -- -109.20  81.00 154.81   26
 62  \w    -92.00 -66.00   1.00    1.00    -- -109.20  77.00-120.00   26
 63  \w   -156.00-127.00   1.00    1.00    -- -109.20 -72.00-132.35   29
;
_diffrn_measurement_device       'AFC12: Kappa 4 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P100K'
_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      0.0300720000
_diffrn_orient_matrix_UB_12      0.0423487000
_diffrn_orient_matrix_UB_13      0.0576382000
_diffrn_orient_matrix_UB_21      0.0516922000
_diffrn_orient_matrix_UB_22      0.0622185000
_diffrn_orient_matrix_UB_23      -0.0383874000
_diffrn_orient_matrix_UB_31      -0.1429628000
_diffrn_orient_matrix_UB_32      0.0314152000
_diffrn_orient_matrix_UB_33      -0.0017617000
_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  0.0384
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            50310
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        66.880
_diffrn_reflns_theta_max         66.880
_diffrn_reflns_theta_min         3.070
_diffrn_source                   'Rotating Anode'
_diffrn_source_type              'Rigaku MM-007HF'
_exptl_absorpt_coefficient_mu    0.951
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92542
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.82a (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    1.379
_exptl_crystal_description       rod
_exptl_crystal_F_000             1808
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform'
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.116
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 3107 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     569
_refine_ls_number_reflns         7389
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0257
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0382P)^2^+0.5087P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0673
_refine_ls_wR_factor_ref         0.0677
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                7225
_reflns_number_total             7389
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05470e2.cif
_cod_data_source_block           16
_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 1570358--1570360.cif.
;
_cod_original_sg_symbol_H-M      P212121
_cod_database_code               1570360
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.658
_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
 N43-H43 = N13-H13
 0.98 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C10(H10), C40(H40)
3.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C14(H14A,H14B), C24(H24A,H24B), C39(H39A,H39B),
 C41(H41A,H41B), C44(H44A,H44B), C54(H54A,H54B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C34(H34), C35(H35), C36(H36), C37(H37), C46(H46), C47(H47), C48(H48),
  C49(H49), C50(H50)
3.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C55(H55A,H55B,H55C)
;
_shelx_res_checksum              65634
_shelx_hkl_checksum              96363