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_1570084
_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         'C16 H21 N O3 S'
_chemical_formula_sum            'C16 H21 N O3 S'
_chemical_formula_weight         307.40
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-05-04 deposited with the CCDC.	2023-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                72.8400(10)
_cell_angle_beta                 81.8890(10)
_cell_angle_gamma                75.0620(10)
_cell_formula_units_Z            2
_cell_length_a                   5.88370(10)
_cell_length_b                   9.30100(10)
_cell_length_c                   14.8817(2)
_cell_measurement_reflns_used    9522
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.8490
_cell_measurement_theta_min      3.0920
_cell_volume                     749.973(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_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      100.01(10)
_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 0.947
_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   -119.00 -23.00   0.50    0.05    --  -46.75 -77.00 -21.00  192
  2  \w    -30.00  29.00   0.50    0.05    --  -46.75  19.00  60.00  118
  3  \w    -51.00 -16.00   0.50    0.05    --  -88.50  45.00 -30.00   70
  4  \w    -51.00 -16.00   0.50    0.05    --  -88.50  45.00 -90.00   70
  5  \w    -51.00 -16.00   0.50    0.05    --  -88.50  45.00 -60.00   70
  6  \w    -51.00 -16.00   0.50    0.05    --  -88.50  45.00  60.00   70
  7  \w    -51.00 -16.00   0.50    0.05    --  -88.50  45.00  90.00   70
  8  \w    -70.00  26.00   0.50    0.05    --  -46.75  77.00 104.00  192
  9  \w     23.00 119.00   0.50    0.05    --   46.75  77.00 104.00  192
 10  \w     83.00 178.00   0.50    0.05    --  106.69  77.00 104.00  190
 11  \w     34.00 101.00   0.50    0.05    --  106.69 -77.00 -21.00  134
 12  \w     34.00 107.00   0.50    0.05    --  106.69-106.00  54.45  146
 13  \w     34.00 105.00   0.50    0.05    --  106.69 -94.00 150.00  142
 14  \w     34.00  71.00   0.50    0.05    --  106.69 -61.00 120.00   74
 15  \w     34.00 105.00   0.50    0.05    --  106.69 -94.00 120.00  142
 16  \w     34.00 111.00   0.50    0.05    --  106.69-125.00 120.00  154
 17  \w     34.00 105.00   0.50    0.05    --  106.69 -94.00 -60.00  142
 18  \w     34.00 101.00   0.50    0.05    --  106.69 -77.00-150.00  134
 19  \w     34.00  71.00   0.50    0.05    --  106.69 -61.00-120.00   74
 20  \w     34.00 105.00   0.50    0.05    --  106.69 -94.00-150.00  142
 21  \w     34.00 101.00   0.50    0.05    --  106.69 -77.00-120.00  134
 22  \w     31.00 122.00   0.50    0.05    --   46.75  19.00   0.00  182
 23  \w     91.00 178.00   0.50    0.05    --  106.69  61.00-180.00  174
 24  \w     31.00 119.00   0.50    0.05    --   46.75  55.00-139.99  176
 25  \w     31.00 119.00   0.50    0.05    --   46.75  55.00 -55.83  176
 26  \w     33.00 120.00   0.50    0.05    --   46.75  43.00  53.47  174
 27  \w     32.00 119.00   0.50    0.05    --   46.75  52.00 -91.50  174
 28  \w     32.00 121.00   0.50    0.05    --   46.75  37.00-180.00  178
 29  \w     31.00 119.00   0.50    0.05    --   46.75  55.00  68.76  176
 30  \w    -25.00  71.00   0.50    0.05    --   46.75 -77.00 -21.00  192
 31  \w   -101.00 -15.00   0.50    0.05    --  -88.50  77.00 104.00  172
 32  \w   -119.00 -83.00   0.50    0.05    --  -46.75 -57.00 -90.00   72
 33  \w   -160.00 -65.00   0.50    0.05    --  -88.50 -77.00 -21.00  190
 34  \w   -119.00 -88.00   0.50    0.05    --  -46.75-125.00 150.00   62
 35  \w   -160.00-101.00   0.50    0.05    --  -88.50 -77.00 120.00  118
 36  \w   -160.00-101.00   0.50    0.05    --  -88.50 -77.00   0.00  118
 37  \w   -160.00-101.00   0.50    0.05    --  -88.50 -77.00-120.00  118
 38  \w   -160.00 -88.00   0.50    0.05    --  -88.50-125.00 -60.00  144
 39  \w   -160.00-101.00   0.50    0.05    --  -88.50 -77.00  30.00  118
;
_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      -0.2014516000
_diffrn_orient_matrix_UB_12      -0.0547831000
_diffrn_orient_matrix_UB_13      0.0687746000
_diffrn_orient_matrix_UB_21      0.0180063000
_diffrn_orient_matrix_UB_22      0.1058408000
_diffrn_orient_matrix_UB_23      0.0599043000
_diffrn_orient_matrix_UB_31      -0.1813738000
_diffrn_orient_matrix_UB_32      0.1322963000
_diffrn_orient_matrix_UB_33      -0.0589785000
_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  0.0461
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            13752
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.355
_diffrn_reflns_theta_min         3.116
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.002
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.388
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
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    1.361
_exptl_crystal_description       plate
_exptl_crystal_F_000             328
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.567
_refine_diff_density_min         -0.626
_refine_diff_density_rms         0.057
_refine_ls_extinction_coef       0.0040(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2989
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0384
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0469P)^2^+0.5202P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0996
_refine_ls_wR_factor_ref         0.1014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2788
_reflns_number_total             2989
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04727j2.cif
_cod_data_source_block           hpd490
_cod_depositor_comments
'Adding full bibliography for 1570081--1570086.cif.'
_cod_database_code               1570084
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     'HDC 414-3'
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.713
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C9(H9A,H9B), C8(H8A,H8B), C12(H12A,H12B),
 C11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C6(H6), C4(H4), C2(H2), C3(H3), C5(H5)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              66022
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.014
_oxdiff_exptl_absorpt_empirical_full_min 0.720