Synthesis of <i>S</i>-allylic sulfinamides by the catalytic nucleophilic allylation of <i>N</i>-sulfinylamines.
Fanai-Danesh, Shamim; Moseley, Daniel F.; Foote, Kevin M.; Jones, Kieran D.; Argent, Stephen P.; Lam, Hon Wai; Organic & biomolecular chemistry 23 (2025) 10502–10507; doi:10.1039/d5ob01562f

data_7160837
_publ_section_title
;
 Synthesis of <i>S</i>-allylic sulfinamides by the catalytic nucleophilic
 allylation of <i>N</i>-sulfinylamines.
;
_journal_issue                   46
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10502
_journal_page_last               10507
_journal_paper_doi               10.1039/d5ob01562f
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H23 N O S'
_chemical_formula_sum            'C23 H23 N O S'
_chemical_formula_weight         361.48
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-09-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-23 deposited with the CCDC.	2025-10-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   14.21800(10)
_cell_length_b                   18.75080(10)
_cell_length_c                   28.9297(2)
_cell_measurement_reflns_used    47268
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      72.4770
_cell_measurement_theta_min      3.8260
_cell_volume                     7712.63(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.2349
_diffrn_detector_type            'Agilent Diffraction Atlas S2 detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -83.00  -6.00   1.00    5.00    --  -41.70 125.00 120.00   77
  2  \w   -116.00 -17.00   1.00    5.00    --  -41.70 -38.00 150.00   99
  3  \w   -111.00 -18.00   1.00    5.00    --  -41.70 -38.00 -30.00   93
  4  \w    -98.00  -6.00   1.00    5.00    --  -41.70 125.00 -90.00   92
  5  \w    -20.00  29.00   1.00    5.00    --  -41.70  38.00 -90.00   49
  6  \w   -103.00 -44.00   1.00    5.00    --  -41.70 -57.00  90.00   59
  7  \w   -111.00 -14.00   1.00    5.00    --  -41.70 -57.00 -90.00   97
  8  \w    -41.00 -14.00   1.00    5.00    --  -41.70 -57.00  90.00   27
  9  \w    -39.00  31.00   1.00    5.00    --  -41.70  57.00  60.00   70
 10  \w      8.00  33.00   1.00    5.00    --   41.70  84.00 -77.39   25
 11  \w     12.00  42.00   1.00    5.00    --   41.70  82.00  20.77   30
 12  \w     11.00  40.00   1.00    5.00    --   41.70  82.00 144.50   29
 13  \w     10.00  40.00   1.00    5.00    --   41.70  80.00  98.92   30
 14  \w      8.00  34.00   1.00    5.00    --   41.70  81.00 -44.81   26
 15  \w     10.00  39.00   1.00    5.00    --   41.70  79.00-134.47   29
 16  \w     73.00  99.00   1.00   20.00    --  104.05  69.00  69.74   26
 17  \w    121.00 176.00   1.00   20.00    --  104.05  68.00  -5.76   55
 18  \w     74.00 100.00   1.00   20.00    --  104.05  67.00-107.94   26
 19  \w     74.00 110.00   1.00   20.00    --  104.05  68.00  -5.76   36
 20  \w     76.00 107.00   1.00   20.00    --  104.05  55.00  25.46   31
 21  \w     75.00 102.00   1.00   20.00    --  104.05  60.00 131.23   27
 22  \w     73.00  99.00   1.00   20.00    --  104.05  71.00 169.38   26
 23  \w     73.00  99.00   1.00   20.00    --  104.05  70.00 -19.27   26
 24  \w    151.00 178.00   1.00   20.00    --  104.05  70.00 -19.27   27
 25  \w     73.00 100.00   1.00   20.00    --  104.05  71.00 -53.46   27
 26  \w    119.00 178.00   1.00   20.00    --  104.05  71.00 -53.46   59
 27  \w     73.00  99.00   1.00   20.00    --  104.05  71.00 160.33   26
 28  \w    143.00 178.00   1.00   20.00    --  104.05  71.00 160.33   35
 29  \w     75.00 176.00   1.00   20.00    --  104.05  62.00 -76.10  101
 30  \w     33.00 120.00   1.00   20.00    --  104.05-135.00  33.01   87
 31  \w     74.00 103.00   1.00   20.00    --  104.05  66.00  93.35   29
 32  \w     74.00 100.00   1.00   20.00    --  104.05  64.00 -52.46   26
 33  \w     75.00 104.00   1.00   20.00    --  104.05  60.00 -18.81   29
 34  \w     72.00  98.00   1.00   20.00    --  104.05  74.00 176.38   26
 35  \w    112.00 177.00   1.00   20.00    --  104.05  74.00-155.92   65
 36  \w     74.00 100.00   1.00   20.00    --  104.05  68.00 130.14   26
 37  \w     72.00 162.00   1.00   20.00    --  104.05  74.00  95.73   90
 38  \w     37.00 103.00   1.00   20.00    --  104.05 -94.00  60.00   66
 39  \w     33.00  93.00   1.00   20.00    --  104.05 -61.00-120.00   60
 40  \w     75.00 174.00   1.00   20.00    --  104.05  61.00 150.00   99
 41  \w     75.00 110.00   1.00   20.00    --  104.05  61.00  30.00   35
 42  \w     75.00 101.00   1.00   20.00    --  104.05  61.00 -30.00   26
 43  \w    129.00 176.00   1.00   20.00    --  104.05  61.00 -30.00   47
 44  \w     72.00  98.00   1.00   20.00    --  104.05  74.00-155.92   26
 45  \w     76.00 146.00   1.00   20.00    --  104.05  61.00 -90.00   70
 46  \w     21.00  64.00   1.00   20.00    --  104.05 -94.00 120.00   43
 47  \w     82.00 107.00   1.00   20.00    --  104.05 -94.00 120.00   25
 48  \w     75.00 101.00   1.00   20.00    --  104.05  61.00-120.00   26
 49  \w     75.00 101.00   1.00   20.00    --  104.05  61.00 -60.00   26
 50  \w     75.00 101.00   1.00   20.00    --  104.05  61.00  90.00   26
 51  \w     51.00 112.00   1.00   20.00    --  104.05-125.00 -60.00   61
 52  \w     35.00 127.00   1.00   20.00    --  104.05 -77.00 120.00   92
 53  \w     74.00 119.00   1.00   20.00    --  104.05  65.00-153.01   45
 54  \w     74.00 100.00   1.00   20.00    --  104.05  67.00-115.25   26
 55  \w     59.00 107.00   1.00   20.00    --  104.05 -94.00   0.00   48
 56  \w     73.00 159.00   1.00   20.00    --  104.05  71.00  37.93   86
 57  \w     76.00 101.00   1.00   20.00    --  104.05  58.00-154.19   25
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0169329000
_diffrn_orient_matrix_UB_12      -0.0807795000
_diffrn_orient_matrix_UB_13      0.0051189000
_diffrn_orient_matrix_UB_21      0.1058283000
_diffrn_orient_matrix_UB_22      0.0114532000
_diffrn_orient_matrix_UB_23      -0.0087119000
_diffrn_orient_matrix_UB_31      0.0160214000
_diffrn_orient_matrix_UB_32      0.0098566000
_diffrn_orient_matrix_UB_33      0.0522646000
_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  0.0417
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            119563
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.251
_diffrn_reflns_theta_min         3.464
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    1.562
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.602
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (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    1.245
_exptl_crystal_description       block
_exptl_crystal_F_000             3072
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: MeOH, CDCl3'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.708
_refine_diff_density_min         -0.289
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 6014 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     953
_refine_ls_number_reflns         14109
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0324
_refine_ls_R_factor_gt           0.0311
_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^)+(0.0515P)^2^+1.7798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0831
_refine_ls_wR_factor_ref         0.0841
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                13687
_reflns_number_total             14109
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01562f2.cif
_cod_data_source_block           sfhwla
_cod_depositor_comments          'Adding full bibliography for 7160837.cif.'
_cod_database_code               7160837
_nottingham_internal_coll_name   SFHWLA
_nottingham_internal_coll_number 19890
_nottingham_internal_coll_client SFD/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '20.00, 5.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczkj1
_nottingham_internal_coll_date   17/09/2024
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 18/09/2024
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 24/09/2024
_nottingham_internal_solution_user pczkj1
_nottingham_internal_refinement_date 24/09/2024
_nottingham_internal_refinement_user pczkj1
_nottingham_internal_validation_date pczspa
_nottingham_internal_validation_user 25/09/2024
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C23SONH23
_chemical_oxdiff_usercomment
'SFHWLA #19890 GVB-2041 SF/HWL fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.678
_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. Restrained distances
 N1A-H1A
 0.88 with sigma of 0.02
 N1B-H1B
 0.88 with sigma of 0.02
 N1C-H1C
 0.88 with sigma of 0.02
 N1D-H1D
 0.88 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C4A(H4A), C4B(H4B), C4C(H4C), C4D(H4D)
3.b Aromatic/amide H refined with riding coordinates:
 C6A(H6A), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A), C14A(H14A),
 C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A), C22A(H22A),
 C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A), C6B(H6B), C10B(H10B),
 C11B(H11B), C12B(H12B), C13B(H13B), C14B(H14B), C16B(H16B), C17B(H17B),
 C18B(H18B), C19B(H19B), C20B(H20B), C22B(H22B), C23B(H23B), C24B(H24B),
 C25B(H25B), C26B(H26B), C6C(H6C), C10C(H10C), C11C(H11C), C12C(H12C),
 C13C(H13C), C14C(H14C), C16C(H16C), C17C(H17C), C18C(H18C), C19C(H19C),
 C20C(H20C), C22C(H22C), C23C(H23C), C24C(H24C), C25C(H25C), C26C(H26C),
 C6D(H6D), C10D(H10D), C11D(H11D), C12D(H12D), C13D(H13D), C14D(H14D),
 C16D(H16D), C17D(H17D), C18D(H18D), C19D(H19D), C20D(H20D), C22D(H22D),
 C23D(H23D), C24D(H24D), C25D(H25D), C26D(H26D)
3.c X=CH2 refined with riding coordinates:
 C7A(H7Aa,H7Ab), C7B(H7Ba,H7Bb), C7C(H7Ca,H7Cb), C7D(H7Da,H7Db)
3.d Idealised Me refined as rotating group:
 C5A(H5Aa,H5Ab,H5Ac), C5B(H5Ba,H5Bb,H5Bc), C5C(H5Ca,H5Cb,H5Cc), C5D(H5Da,H5Db,
 H5Dc)
;
_shelx_res_checksum              43184
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.429
_oxdiff_exptl_absorpt_empirical_full_min 0.708