Visible-light-induced bifunctionalisation of (homo)propargylic amines with CO<sub>2</sub> and arylsulfinates.
Reddy, Mandapati Bhargava; McGarrigle, Eoghan M.; Chemical communications (Cambridge, England)  (2023) –; doi:10.1039/d3cc04160c

data_7132291
_publ_section_title
;
 Visible-light-induced bifunctionalisation of (homo)propargylic amines
 with CO<sub>2</sub> and arylsulfinates.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d3cc04160c
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H19 N O4 S'
_chemical_formula_sum            'C19 H19 N O4 S'
_chemical_formula_weight         357.41
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-15
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2023-08-08 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.37430(10)
_cell_length_b                   15.0097(2)
_cell_length_c                   15.6382(2)
_cell_measurement_reflns_used    10586
_cell_measurement_temperature    104.60(14)
_cell_measurement_theta_max      72.5330
_cell_measurement_theta_min      2.8060
_cell_volume                     1730.93(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (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      104.60(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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   -126.00  37.00   1.00    1.00    --  -42.33 -10.00-114.00  163
  2  \w    100.00 177.00   1.00    1.98    --  104.49 120.00-136.00   77
  3  \w     97.00 177.00   1.00    1.98    --  104.49 126.00 129.00   80
  4  \w   -116.00 -58.00   1.00    1.00    --  -42.33-153.00 -19.00   58
  5  \w     27.00  96.00   1.00    1.00    --   42.33-125.00-120.00   69
  6  \w     31.00 109.00   1.00    1.98    --  104.49-111.00  90.00   78
  7  \w    104.00 178.00   1.00    1.98    --  104.49 111.00 -90.00   74
  8  \w     31.00 109.00   1.00    1.98    --  104.49-111.00  60.00   78
  9  \w     31.00 130.00   1.00    1.98    --  104.49 -45.00-150.00   99
 10  \w     25.00 178.00   1.00    1.98    --  104.49  10.00  59.00  153
 11  \w   -115.00 -14.00   1.00    1.00    --  -42.33 -57.00 150.00  101
 12  \w   -115.00 -14.00   1.00    1.00    --  -42.33 -57.00-150.00  101
 13  \w   -115.00 -65.00   1.00    1.00    --  -42.33-143.00-116.00   50
 14  \w   -115.00 -14.00   1.00    1.00    --  -42.33 -57.00  60.00  101
 15  \w     31.00 109.00   1.00    1.98    --  104.49-111.00-120.00   78
 16  \w     79.00 127.00   1.00    1.98    --  104.49  45.00 120.00   48
 17  \w     76.00 178.00   1.00    1.98    --  104.49  30.00-150.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0242635000
_diffrn_orient_matrix_UB_12      -0.1019095000
_diffrn_orient_matrix_UB_13      -0.0014049000
_diffrn_orient_matrix_UB_21      -0.0125053000
_diffrn_orient_matrix_UB_22      -0.0020915000
_diffrn_orient_matrix_UB_23      0.0983457000
_diffrn_orient_matrix_UB_31      -0.2071235000
_diffrn_orient_matrix_UB_32      -0.0117318000
_diffrn_orient_matrix_UB_33      -0.0060875000
_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  0.0314
_diffrn_reflns_av_unetI/netI     0.0213
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            16147
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.637
_diffrn_reflns_theta_min         4.082
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.867
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.426
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.75a (Rigaku Oxford Diffraction, 2022)
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            'metallic dark yellow'
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1313 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3386
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0376P)^2^+0.2550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0682
_refine_ls_wR_factor_ref         0.0703
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                3225
_reflns_number_total             3386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04160c3.cif
_cod_data_source_block           exp_1231_BR-2-66A
_cod_database_code               7132291
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C19H19NO4S
_chemical_oxdiff_usercomment     BR-2-66A_BhargavaReddy_McGarribleGroup
_shelx_estimated_absorpt_t_max   0.767
_shelx_estimated_absorpt_t_min   0.569
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C14(H14), C15(H15), C17(H17),
 C18(H18)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              49985
_shelx_hkl_checksum              68283
_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 1.967
_oxdiff_exptl_absorpt_empirical_full_min 0.574