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_1570086
_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_absolute_configuration ad
_chemical_formula_moiety         'C35 H53 N O2 S'
_chemical_formula_sum            'C35 H53 N O2 S'
_chemical_formula_weight         551.84
_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             2022-03-29
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.1503(2)
_cell_length_b                   19.7477(4)
_cell_length_c                   25.7609(4)
_cell_measurement_reflns_used    17868
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.0980
_cell_measurement_theta_min      2.8230
_cell_volume                     7198.5(2)
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.977
_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    -38.00  28.00   0.50    1.16    --  -46.87  31.00 -77.00  132
  2  \w    -30.00  29.00   0.50    1.16    --  -46.87  19.00  60.00  118
  3  \w    -81.00 -15.00   0.50    4.64    --  -88.50 101.00 117.00  132
  4  \w   -122.00 -31.00   0.50    1.16    --  -46.87 -19.00  90.00  182
  5  \w   -120.00 -87.00   0.50    1.16    --  -46.87-125.00 -90.00   66
  6  \w   -121.00 -96.00   0.50    1.16    --  -46.87 -37.00 -30.00   50
  7  \w     34.00 106.00   0.50    4.64    --  106.69-105.00 -79.00  144
  8  \w     34.00 111.00   0.50    4.64    --  106.69-125.00   0.00  154
  9  \w     34.00 101.00   0.50    4.64    --  106.69 -77.00 150.00  134
 10  \w     34.00 101.00   0.50    4.64    --  106.69 -77.00   0.00  134
 11  \w     34.00  71.00   0.50    4.64    --  106.69 -61.00 -90.00   74
 12  \w     34.00  71.00   0.50    4.64    --  106.69 -61.00-150.00   74
 13  \w     91.00 178.00   0.50    4.64    --  106.69  31.00 -77.00  174
;
_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      -0.0398840000
_diffrn_orient_matrix_UB_12      0.0655447000
_diffrn_orient_matrix_UB_13      -0.0237513000
_diffrn_orient_matrix_UB_21      -0.0160913000
_diffrn_orient_matrix_UB_22      -0.0370308000
_diffrn_orient_matrix_UB_23      -0.0519509000
_diffrn_orient_matrix_UB_31      -0.1000199000
_diffrn_orient_matrix_UB_32      -0.0203389000
_diffrn_orient_matrix_UB_33      0.0177770000
_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  0.0430
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            38698
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.474
_diffrn_reflns_theta_min         2.819
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.993
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.521
_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    1.018
_exptl_crystal_description       plank
_exptl_crystal_F_000             2416
_exptl_crystal_size_max          0.215
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.809
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 5064 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.100(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     721
_refine_ls_number_reflns         14140
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0698
_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^+16.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1577
_reflns_Friedel_coverage         0.751
_reflns_Friedel_fraction_full    0.943
_reflns_Friedel_fraction_max     0.884
_reflns_number_gt                13023
_reflns_number_total             14140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04727j2.cif
_cod_data_source_block           hpd528
_cod_depositor_comments
'Adding full bibliography for 1570081--1570086.cif.'
_cod_original_cell_volume        7198.51(19)
_cod_database_code               1570086
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     'HDC 412-5'
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.815
_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, All C(H,H,H,H) groups, All O(H) groups
2. Restrained distances
 H2A-O1_$1
 1.9 with sigma of 0.02
 H2A-O2
 1.05 with sigma of 0.02
3.a Riding coordinates:
 N1(H1)
3.b Ternary CH refined with riding coordinates:
 C45(H45), C51(H51), C41(H41), C16(H16), C10(H10), C49(H49), C14(H14), C6(H6)
3.c Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C52(H52A,H52B), C57(H57A,H57B), C38(H38A,H38B), C56(H56A,
 H56B), C53(H53A,H53B), C48(H48A,H48B), C47(H47A,H47B), C40(H40A,H40B),
 C12(H12A,H12B), C13(H13A,H13B), C17(H17A,H17B), C22(H22A,H22B), C2(H2B,H2C),
 C18(H18A,H18B), C44(H44A,H44B), C21(H21A,H21B), C9(H9A,H9B), C3(H3A,H3B),
 C5(H5A,H5B)
3.d Aromatic/amide H refined with riding coordinates:
 N2(H2), C59(H59), C24(H24), C43(H43), C63(H63), C61(H61), C25(H25), C8(H8),
 C60(H60), C62(H62), C26(H26), C28(H28), C27(H27)
3.e Idealised Me refined as rotating group:
 C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C66(H66A,H66B,H66C), C67(H67A,H67B,
 H67C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C68(H68A,H68B,H68C), C34(H34A,
 H34B,H34C), C35(H35A,H35B,H35C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C), C30(H30A,H30B,H30C), C29(H29A,H29B,H29C)
3.f Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              91153
_shelx_fab_checksum              82479
_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 1.406
_oxdiff_exptl_absorpt_empirical_full_min 0.807