Kinetically-driven reactivity of sulfinylamines enables direct conversion of carboxylic acids to sulfinamides.
Dang, Hang T.; Porey, Arka; Nand, Sachchida; Trevino, Ramon; Manning-Lorino, Patrick; Hughes, William B.; Fremin, Seth O.; Thompson, William T.; Dhakal, Shree Krishna; Arman, Hadi D.; Larionov, Oleg V.; Chemical science 14 (2023) 13384–13391; doi:10.1039/d3sc04727j

data_1570085
_publ_section_title
;
 Kinetically-driven reactivity of sulfinylamines enables direct conversion
 of carboxylic acids to sulfinamides.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              13384
_journal_page_last               13391
_journal_paper_doi               10.1039/d3sc04727j
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C12 H17 N O S'
_chemical_formula_sum            'C12 H17 N O S'
_chemical_formula_weight         223.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-13
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2022-05-04 deposited with the CCDC.	2023-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                95.121(3)
_cell_angle_beta                 91.181(3)
_cell_angle_gamma                105.039(3)
_cell_formula_units_Z            2
_cell_length_a                   6.1241(2)
_cell_length_b                   8.1468(2)
_cell_length_c                   11.8684(4)
_cell_measurement_reflns_used    5592
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      74.5790
_cell_measurement_theta_min      3.7320
_cell_volume                     568.98(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.955
_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    -30.00  30.00   0.50    0.05    --   45.95 -19.00  60.00  120
  2  \w     83.00 119.00   0.50    0.05    --   45.95  57.00  60.00   72
  3  \w     81.00 169.00   0.50    0.05    --  106.87 146.00  29.00  176
  4  \w     96.00 178.00   0.50    0.05    --  106.87 124.00-136.00  164
  5  \w    101.00 178.00   0.50    0.05    --  106.87  77.00-180.00  154
  6  \w    101.00 178.00   0.50    0.05    --  106.87  77.00-150.00  154
  7  \w     90.00 178.00   0.50    0.05    --  106.87  45.00 -30.00  176
  8  \w     34.00  95.00   0.50    0.05    --   45.95-124.00 144.00  122
  9  \w     34.00 111.00   0.50    0.05    --  106.87-124.00 144.00  154
 10  \w     46.00 108.00   0.50    0.05    --   45.95-146.00 -21.00  124
 11  \w     46.00 127.00   0.50    0.05    --  106.87-146.00 -21.00  162
 12  \w     34.00 101.00   0.50    0.05    --  106.87 -77.00 150.00  134
 13  \w     34.00 106.00   0.50    0.05    --  106.87 -94.00  30.00  144
 14  \w     34.00 106.00   0.50    0.05    --  106.87 -94.00 -90.00  144
 15  \w     34.00  71.00   0.50    0.05    --  106.87 -61.00-150.00   74
 16  \w     34.00 106.00   0.50    0.05    --  106.87 -94.00 -60.00  144
 17  \w     34.00 101.00   0.50    0.05    --  106.87 -77.00 -60.00  134
 18  \w     34.00  71.00   0.50    0.05    --  106.87 -61.00   0.00   74
 19  \w     34.00 106.00   0.50    0.05    --  106.87 -94.00 150.00  144
 20  \w    -85.00 -12.00   0.50    0.05    --  -45.95 124.00-136.00  146
 21  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00-180.00   72
 22  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00-150.00   72
 23  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00 -90.00   72
 24  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00-120.00   72
 25  \w    -85.00 -15.00   0.50    0.05    --  -88.50 124.00-136.00  140
 26  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00   0.00   72
 27  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00  60.00   72
 28  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00  90.00   72
 29  \w    -51.00 -15.00   0.50    0.05    --  -88.50  45.00 150.00   72
 30  \w   -101.00 -24.00   0.50    0.05    --  -45.95 146.00  29.00  154
 31  \w   -121.00 -28.00   0.50    0.05    --  -45.95 -37.00 150.00  186
 32  \w   -118.00 -59.00   0.50    0.05    --  -45.95-146.00 -21.00  118
 33  \w   -118.00 -83.00   0.50    0.05    --  -45.95 -57.00   0.00   70
 34  \w   -118.00 -83.00   0.50    0.05    --  -45.95 -57.00 -60.00   70
 35  \w   -118.00 -83.00   0.50    0.05    --  -45.95 -57.00-120.00   70
 36  \w   -118.00 -83.00   0.50    0.05    --  -45.95 -57.00-150.00   70
 37  \w   -121.00 -28.00   0.50    0.05    --  -45.95 -37.00 -90.00  186
 38  \w   -118.00 -83.00   0.50    0.05    --  -45.95 -57.00  90.00   70
 39  \w   -121.00 -28.00   0.50    0.05    --  -45.95 -37.00  30.00  186
 40  \w   -121.00 -73.00   0.50    0.05    --  -45.95 -37.00 -30.00   96
 41  \w   -152.00 -59.00   0.50    0.05    --  -88.50-146.00 -21.00  186
 42  \w   -118.00 -88.00   0.50    0.05    --  -45.95-125.00-180.00   60
 43  \w   -161.00 -91.00   0.50    0.05    --  -88.50 -61.00-150.00  140
 44  \w   -161.00 -91.00   0.50    0.05    --  -88.50 -61.00 -90.00  140
 45  \w   -161.00 -74.00   0.50    0.05    --  -88.50-124.00 144.00  174
 46  \w   -161.00 -91.00   0.50    0.05    --  -88.50 -61.00 150.00  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0169575000
_diffrn_orient_matrix_UB_12      -0.0009505000
_diffrn_orient_matrix_UB_13      -0.1297572000
_diffrn_orient_matrix_UB_21      0.2278739000
_diffrn_orient_matrix_UB_22      -0.0463808000
_diffrn_orient_matrix_UB_23      -0.0086062000
_diffrn_orient_matrix_UB_31      -0.1256024000
_diffrn_orient_matrix_UB_32      -0.1912059000
_diffrn_orient_matrix_UB_33      -0.0104217000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10808
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.928
_diffrn_reflns_theta_min         3.743
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.298
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.491
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.304
_exptl_crystal_description       plate
_exptl_crystal_F_000             240
_exptl_crystal_size_max          0.178
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.561
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         2266
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0500P)^2^+0.3500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.0985
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2127
_reflns_number_total             2266
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04727j2.cif
_cod_data_source_block           hpd467
_cod_depositor_comments
'Adding full bibliography for 1570081--1570086.cif.'
_cod_database_code               1570085
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     'HDC 376-CO'
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.685
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C9(H9A,H9B), C8(H8A,H8B), C12(H12A,H12B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C2(H2), C4(H4), C5(H5), C3(H3)
;
_shelx_res_checksum              95954
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.216
_oxdiff_exptl_absorpt_empirical_full_min 0.770