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_1570359
_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 H21 Cl F2 N2 O5'
_chemical_formula_sum            'C23 H21 Cl F2 N2 O5'
_chemical_formula_weight         478.87
_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             2023-10-02
_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            4
_cell_length_a                   9.32874(6)
_cell_length_b                   14.99320(9)
_cell_length_c                   16.18409(11)
_cell_measurement_reflns_used    23699
_cell_measurement_temperature    125
_cell_measurement_theta_max      75.2730
_cell_measurement_theta_min      4.0110
_cell_volume                     2263.63(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection
'CrystalClear-SM Expert 2.1 b45 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.994
_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   -125.00  55.00   0.50   10.00    --  -35.00  60.00 -45.00  360
  2  \w   -108.00 -48.00   0.50   10.00    --  -35.00  30.00  90.00  120
  3  \w   -173.50 -10.00   0.50   20.00    -- -100.00  60.00 -90.00  327
  4  \w   -187.00 -40.00   0.50   20.00    -- -100.00  30.00  45.00  294
  5  \w   -165.00 -10.00   0.50   20.00    -- -100.00  60.00-180.00  310
  6  \w   -190.00-127.50   0.50   20.00    -- -100.00  60.00 135.00  125
  7  \w   -165.00 -19.00   0.50   20.00    -- -100.00  60.00   0.00  292
  8  \w   -152.50 -44.50   0.50   20.00    -- -100.00  30.00 135.00  216
  9  \w   -174.00-114.00   0.50   20.00    -- -100.00  60.00  90.00  120
 10  \w    -70.00 -10.00   0.50   20.00    -- -100.00  30.00   0.00  120
 11  \w   -190.00 -10.00   0.50   20.00    -- -100.00  30.00 -90.00  360
 12  \w   -174.00 -10.00   0.50   20.00    -- -100.00  60.00  45.00  328
 13  \w   -190.00-120.00   0.50   20.00    -- -100.00  60.00-135.00  140
;
_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      -0.0220372000
_diffrn_orient_matrix_UB_12      0.0810441000
_diffrn_orient_matrix_UB_13      0.0570913000
_diffrn_orient_matrix_UB_21      0.0033438000
_diffrn_orient_matrix_UB_22      0.0624137000
_diffrn_orient_matrix_UB_23      -0.0755927000
_diffrn_orient_matrix_UB_31      -0.1636532000
_diffrn_orient_matrix_UB_32      -0.0096910000
_diffrn_orient_matrix_UB_33      -0.0092255000
_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  0.0230
_diffrn_reflns_av_unetI/netI     0.0127
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            26847
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.471
_diffrn_reflns_theta_min         4.019
_diffrn_source                   'Rotating Anode'
_diffrn_source_type              'Rigaku MM-007HF'
_exptl_absorpt_coefficient_mu    1.976
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86671
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
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    1.405
_exptl_crystal_description       prism
_exptl_crystal_F_000             992
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.150
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 1936 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         4647
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0254
_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^)+(0.0395P)^2^+0.4158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0676
_refine_ls_wR_factor_ref         0.0678
_reflns_Friedel_coverage         0.754
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                4562
_reflns_number_total             4647
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05470e2.cif
_cod_data_source_block           20
_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               1570359
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.827
_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
 N15-H15
 0.98 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C12(H12)
3.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C16(H16A,H16B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20), C21(H21),
 C22(H22)
3.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              64732
_shelx_hkl_checksum              44237