Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)–MPAA catalyzed C–H arylation and olefination
Mukherjee, Kallol; Grimblat, Nicolas; Sau, Somratan; Ghosh, Koushik; Shankar, Majji; Gandon, Vincent; Sahoo, Akhila K.; Chemical Science  (2021) –; doi:10.1039/D1SC04299H

data_1565106
_publ_section_title
;
 Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)--MPAA
 catalyzed C--H arylation and olefination
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04299H
_journal_year                    2021
_chemical_formula_moiety         'C28 H28 N2 O4 S'
_chemical_formula_sum            'C28 H28 N2 O4 S'
_chemical_formula_weight         488.58
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-06-09 deposited with the CCDC.	2021-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.7073(5)
_cell_length_b                   22.7073(5)
_cell_length_c                   9.0908(2)
_cell_measurement_reflns_used    15371
_cell_measurement_temperature    292(110)
_cell_measurement_theta_max      21.7740
_cell_measurement_theta_min      2.0640
_cell_volume                     4059.42(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_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_environment      air
_diffrn_ambient_temperature      292(110)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.976
_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    -34.00  22.00   0.50   12.00    --  -14.97 -94.00  30.00  112
  2  \w     19.00  69.00   0.50   12.00    --   16.22-125.00   0.00  100
  3  \w     16.00  74.00   0.50   12.00    --   16.22-136.00 -38.00  116
  4  \w    -23.00  42.00   0.50   12.00    --  -14.97  45.00  90.00  130
  5  \w     42.00  68.00   0.50   12.00    --   16.22  45.00  90.00   52
  6  \w    -10.00  90.00   0.50   12.00    --   16.22  30.00  90.00  200
  7  \w     -4.00  21.00   0.50   12.00    --   16.22  45.00  90.00   50
  8  \w    -55.00 -30.00   0.50   12.00    --  -14.97 136.00  26.00   50
  9  \w     45.00  70.00   0.50   12.00    --   16.22-133.00 139.00   50
 10  \w    -33.00  22.00   0.50   12.00    --  -14.97 -94.00 150.00  110
 11  \w    -53.00  34.00   0.50   12.00    --   16.22 -45.00 -90.00  174
 12  \w     41.00  81.00   0.50   12.00    --   16.22  45.00-120.00   80
 13  \w      4.00  29.00   0.50   12.00    --   16.22  45.00-120.00   50
 14  \w    -57.00  -1.00   0.50   12.00    --   16.22 -30.00-180.00  112
 15  \w    -67.00 -42.00   0.50   12.00    --  -14.97 133.00-152.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0358485000
_diffrn_orient_matrix_UB_12      0.0213650000
_diffrn_orient_matrix_UB_13      -0.0007447000
_diffrn_orient_matrix_UB_21      -0.0038668000
_diffrn_orient_matrix_UB_22      0.0286932000
_diffrn_orient_matrix_UB_23      0.0130022000
_diffrn_orient_matrix_UB_31      0.0010128000
_diffrn_orient_matrix_UB_32      -0.0046122000
_diffrn_orient_matrix_UB_33      0.0769152000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0460
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            39105
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.993
_diffrn_reflns_theta_min         2.071
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.154
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67337
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_description       block
_exptl_crystal_F_000             1548
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1331 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     321
_refine_ls_number_reflns         5690
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0831
_refine_ls_R_factor_gt           0.0519
_refine_ls_shift/su_max          0.026
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0785P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1281
_refine_ls_wR_factor_ref         0.1450
_reflns_Friedel_coverage         0.856
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.950
_reflns_number_gt                3797
_reflns_number_total             5690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04299h2.cif
_cod_data_source_block           aks82
_cod_original_cell_volume        4059.4(2)
_cod_database_code               1565106
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.970
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C4(H4), C16(H16), C22(H22), C20(H20), C21(H21), C8(H8),
 C11(H11), C9(H9), C14(H14), C12(H12), C13(H13)
2.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C26(H26A,H26B,
 H26C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              92898
_shelx_hkl_checksum              33566
_shelx_fab_checksum              50201
_olex2_submission_original_sample_id AKS82
_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 1.624
_oxdiff_exptl_absorpt_empirical_full_min 0.633