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_1570083
_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         'C9 H13 Br Cl N3 O2 S'
_chemical_formula_sum            'C9 H13 Br Cl N3 O2 S'
_chemical_formula_weight         342.64
_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             2022-04-14
_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                70.025(7)
_cell_angle_beta                 84.920(8)
_cell_angle_gamma                76.652(9)
_cell_formula_units_Z            2
_cell_length_a                   5.5464(6)
_cell_length_b                   11.0627(10)
_cell_length_c                   11.4651(8)
_cell_measurement_reflns_used    2707
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.9870
_cell_measurement_theta_min      4.1270
_cell_volume                     643.26(11)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.973
_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     73.00  99.00   0.50    0.34    --   46.37  36.00 -92.00   52
  2  \w    102.00 138.00   0.50    1.35    --  106.69  36.00 -92.00   72
  3  \w    101.00 130.00   0.50    1.35    --  106.69  77.00 -60.00   58
  4  \w    147.00 178.00   0.50    1.35    --  106.69  77.00 -60.00   62
  5  \w    143.00 172.00   0.50    1.35    --  106.69  36.00 -92.00   58
  6  \w     91.00 135.00   0.50    1.35    --  106.69  15.00   0.00   88
  7  \w    143.00 178.00   0.50    1.35    --  106.69  15.00   0.00   70
  8  \w     85.00 116.00   0.50    0.34    --   46.37  57.00  90.00   62
  9  \w    -27.00  25.00   0.50    0.34    --   46.37 -19.00  30.00  104
 10  \w    -21.00  41.00   0.50    0.34    --   46.37 -36.00 110.00  124
 11  \w     36.00  70.00   0.50    1.35    --  106.69 -77.00 120.00   68
 12  \w     38.00  70.00   0.50    1.35    --  106.69 -61.00 120.00   64
 13  \w     39.00  71.00   0.50    1.35    --  106.69 -61.00 -90.00   64
 14  \w     35.00 100.00   0.50    1.35    --  106.69 -77.00 -90.00  130
 15  \w     76.00 103.00   0.50    1.35    --  106.69 -94.00-120.00   54
 16  \w     62.00 107.00   0.50    1.35    --  106.69-125.00-120.00   90
 17  \w     36.00  84.00   0.50    0.34    --   46.37-125.00   0.00   96
 18  \w     41.00  68.00   0.50    1.35    --  106.69-125.00 120.00   54
 19  \w     38.00  78.00   0.50    1.35    --  106.69-125.00  60.00   80
 20  \w     82.00 111.00   0.50    1.35    --  106.69-125.00 120.00   58
 21  \w     84.00 110.00   0.50    1.35    --  106.69-125.00  60.00   52
 22  \w     79.00 109.00   0.50    1.35    --  106.69-125.00  30.00   60
 23  \w     43.00  70.00   0.50    1.35    --  106.69-125.00  30.00   54
 24  \w     37.00  63.00   0.50    1.35    --  106.69 -94.00 120.00   52
 25  \w     79.00 105.00   0.50    1.35    --  106.69 -94.00 120.00   52
 26  \w     45.00  71.00   0.50    0.34    --   46.37 -99.00-180.00   52
 27  \w     71.00  97.00   0.50    1.35    --  106.69 -94.00-150.00   52
 28  \w     36.00  61.00   0.50    1.35    --  106.69 -94.00-150.00   50
 29  \w     36.00  72.00   0.50    1.35    --  106.69 -94.00-120.00   72
 30  \w     39.00  73.00   0.50    1.35    --  106.69 -94.00  60.00   68
 31  \w    -69.00 -18.00   0.50    1.35    --  -88.50  61.00  90.00  102
 32  \w    -35.00  26.00   0.50    0.34    --  -46.37  36.00 -92.00  122
 33  \w    -40.00 -14.00   0.50    1.35    --  -88.50  36.00 -92.00   52
 34  \w    -46.00 -18.00   0.50    1.35    --  -88.50  45.00-120.00   56
 35  \w    -49.00 -24.00   0.50    1.35    --  -88.50 125.00-180.00   50
 36  \w    -84.00 -58.00   0.50    1.35    --  -88.50 125.00 -30.00   52
 37  \w   -152.00 -91.00   0.50    1.35    --  -88.50 -36.00 110.00  122
 38  \w   -116.00 -70.00   0.50    0.34    --  -46.37 -36.00 110.00   92
 39  \w   -159.00-108.00   0.50    1.35    --  -88.50 -77.00 -90.00  102
 40  \w   -136.00-100.00   0.50    1.35    --  -88.50 -94.00-150.00   72
 41  \w   -117.00 -88.00   0.50    0.34    --  -46.37-125.00-120.00   58
 42  \w   -116.00 -88.00   0.50    0.34    --  -46.37-125.00  60.00   56
 43  \w     77.00 112.00   0.50    0.34    --   46.37  37.00-150.00   70
 44  \w     -4.00  25.00   0.50    0.34    --   46.37 -19.00-120.00   58
 45  \w   -148.00-104.00   0.50    1.35    --  -88.50 -77.00  60.00   88
 46  \w   -139.00-112.00   0.50    1.35    --  -88.50 -94.00 120.00   54
 47  \w    -66.00 -40.00   0.50    1.35    --  -88.50  61.00 -30.00   52
 48  \w    150.00 177.00   0.50    1.35    --  106.69  15.00 -30.00   54
 49  \w     90.00 126.00   0.50    1.35    --  106.69  15.00 -30.00   72
 50  \w     66.00 105.00   0.50    1.35    --  106.69 -94.00  30.00   78
 51  \w     34.00  64.00   0.50    1.35    --  106.69 -61.00 -30.00   60
 52  \w    153.00 178.00   0.50    1.35    --  106.69  15.00 120.00   50
 53  \w     76.00 101.00   0.50    1.35    --  106.69 -77.00-150.00   50
 54  \w     92.00 133.00   0.50    1.35    --  106.69  15.00 120.00   82
;
_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      -0.0622240000
_diffrn_orient_matrix_UB_12      -0.0896966000
_diffrn_orient_matrix_UB_13      -0.0652046000
_diffrn_orient_matrix_UB_21      -0.2731743000
_diffrn_orient_matrix_UB_22      0.0739582000
_diffrn_orient_matrix_UB_23      -0.0090416000
_diffrn_orient_matrix_UB_31      0.0548271000
_diffrn_orient_matrix_UB_32      0.0974456000
_diffrn_orient_matrix_UB_33      -0.1269237000
_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  0.0642
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7134
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.977
_diffrn_reflns_theta_min         4.354
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.759
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.632
_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    1.769
_exptl_crystal_description       needle
_exptl_crystal_F_000             344
_exptl_crystal_size_max          0.207
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.072
_refine_diff_density_max         1.135
_refine_diff_density_min         -1.104
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         2379
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0876
_refine_ls_R_factor_gt           0.0790
_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^)+(0.0100P)^2^+6.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1741
_refine_ls_wR_factor_ref         0.1791
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2011
_reflns_number_total             2379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04727j2.cif
_cod_data_source_block           hpd534g
_cod_depositor_comments
'Adding full bibliography for 1570081--1570086.cif.'
_cod_database_code               1570083
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S Br Cl'
_chemical_oxdiff_usercomment     'HDc 574-1'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
2. Restrained distances
 C9B-C8B
 1.6 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C8B) = Uanis(C9B) = Uanis(Cl1B)
Uanis(C9A) = Uanis(Cl1A) = Uanis(C8A)
4. Others
 Fixed Sof: Cl1A(0.65) Cl1B(0.35) H7AA(0.65) H7AB(0.65) H7BC(0.35) H7BD(0.35)
 C8A(0.65) H8AA(0.65) H8AB(0.65) C9A(0.65) H9AA(0.65) H9AB(0.65) C8B(0.35)
 H8BA(0.35) H8BB(0.35) C9B(0.35) H9BA(0.35) H9BB(0.35)
5.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7AA,H7AB), C7(H7BC,H7BD), C8A(H8AA,H8AB),
 C9A(H9AA,H9AB), C8B(H8BA,H8BB), C9B(H9BA,H9BB)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C2(H2)
;
_shelx_res_checksum              69711
_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 3.265
_oxdiff_exptl_absorpt_empirical_full_min 0.374