Intermolecular addition of carbon-centered radicals to ynamides - A regio- and stereoselective route to persubstituted α-iodo-enamides.
Dwadnia, Nejib; Lingua, Hugo; Mouysset, Dominique; Mimoun, Liliane; Siri, Didier; Bertrand, Michèle P; Feray, Laurence; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b03255

data_4037996
_publ_section_title
;
 Intermolecular addition of carbon-centered radicals to ynamides - A
 regio- and stereoselective route to persubstituted \a-iodo-enamides.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03255
_journal_year                    2020
_chemical_formula_moiety         'C11 H15 I N2 O2'
_chemical_formula_sum            'C11 H15 I N2 O2'
_chemical_formula_weight         334.15
_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
_audit_creation_date             2019-06-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                72.507(2)
_cell_angle_beta                 76.823(2)
_cell_angle_gamma                87.285(2)
_cell_formula_units_Z            4
_cell_length_a                   9.2857(2)
_cell_length_b                   9.7065(3)
_cell_length_c                   16.1028(4)
_cell_measurement_reflns_used    24901
_cell_measurement_temperature    295
_cell_measurement_theta_max      25.3960
_cell_measurement_theta_min      3.0920
_cell_volume                     1347.45(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      295
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.855
_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    -84.00 -39.00   1.00    7.50    --   -7.98 154.00  92.93   45
  2  \w    -16.00  83.00   1.00    7.50    --    8.25  38.00 -30.00   99
  3  \w    -80.00  96.00   1.00    7.50    --    8.25   0.00  90.00  176
  4  \w    -24.00  84.00   1.00    7.50    --    8.25  77.00-180.00  108
  5  \w    -16.00  83.00   1.00    7.50    --    8.25  38.00 120.00   99
  6  \w    -29.00  48.00   1.00    7.50    --   10.00 -91.00  26.53   77
  7  \w    -17.00  54.00   1.00    7.50    --   10.00-104.00 124.06   71
  8  \w    -17.00  54.00   1.00    7.50    --   10.00-104.00 -54.65   71
  9  \w    -67.00 -27.00   1.00    7.50    --   -7.98 129.00-103.80   40
 10  \w    -20.00  33.00   1.00    7.50    --   -7.98 -99.00 -90.00   53
 11  \w    -65.00 -24.00   1.00    7.50    --   -7.98 126.00-166.55   41
 12  \w    -66.00  33.00   1.00    7.50    --    8.25 -38.00-120.00   99
 13  \w    -20.00  49.00   1.00    7.50    --    8.25 -99.00 150.00   69
 14  \w    -20.00  49.00   1.00    7.50    --    8.25 -99.00  30.00   69
 15  \w    -80.00  96.00   1.00    7.50    --    8.25   0.00-150.00  176
 16  \w    -80.00  96.00   1.00    7.50    --    8.25   0.00-120.00  176
 17  \w    -80.00 -29.00   1.00    7.50    --    8.25   0.00 -90.00   51
 18  \w    -80.00  96.00   1.00    7.50    --    8.25   0.00-180.00  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0238100000
_diffrn_orient_matrix_UB_12      -0.0557436000
_diffrn_orient_matrix_UB_13      -0.0142291000
_diffrn_orient_matrix_UB_21      0.0192880000
_diffrn_orient_matrix_UB_22      0.0443238000
_diffrn_orient_matrix_UB_23      -0.0450081000
_diffrn_orient_matrix_UB_31      0.0722427000
_diffrn_orient_matrix_UB_32      -0.0283087000
_diffrn_orient_matrix_UB_33      -0.0042221000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.855
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            59991
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.228
_diffrn_reflns_theta_min         2.973
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.366
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.647
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.912
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         6247
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0497P)^2^+1.9108P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1259
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4678
_reflns_number_total             6247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03255_si_002.cif
_cod_data_source_block           ndw1105
_cod_depositor_comments
;

2020-03-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        1347.46(6)
_cod_original_formula_moiety     '2(C11 H15 I N2 O2)'
_cod_original_formula_sum        'C22 H30 I2 N4 O4'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     668.30
_cod_database_code               4037996
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.624
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.66
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C21-C22
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C21 \\sim C22: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01
4.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,
 H10B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C19(H19A,H19B),
 C20(H20A,H20B), C21(H21A,H21B)
4.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C22(H22A,H22B,H22C)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.447
_oxdiff_exptl_absorpt_empirical_full_min 0.653