Asymmetric Propargylic Radical Cyanation Enabled by Dual Organophotoredox and Copper Catalysis.
Lu, Fu-Dong; Liu, Dan; Zhu, Lei; Lu, Liang-Qiu; Yang, Qian; Zhou, Quan-Quan; Wei, Yi; Lan, Yu; Xiao, Wen-Jing; Journal of the American Chemical Society 141 (2019) 6167–6172; doi:10.1021/jacs.9b02338

data_4128666
_publ_section_title
;
 Asymmetric Propargylic Radical Cyanation Enabled by Dual Organophotoredox
 and Copper Catalysis.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6167
_journal_page_last               6172
_journal_paper_doi               10.1021/jacs.9b02338
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H15 N'
_chemical_formula_sum            'C18 H15 N'
_chemical_formula_weight         245.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.5540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.22940(10)
_cell_length_b                   7.46190(10)
_cell_length_c                   14.96680(10)
_cell_measurement_reflns_used    24295
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.1820
_cell_measurement_theta_min      3.1640
_cell_volume                     1383.42(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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    -88.00  27.00   0.50    0.50    --    0.00 -38.00-150.00  230
  2  \w     -8.00  46.00   0.50    0.50    --   28.00  79.00  85.93  108
  3  \w     74.00 101.00   0.50    0.50    --   28.00  79.00  85.93   54
  4  \w    -37.00  63.00   0.50    0.50    --   32.00 -66.00  48.28  200
  5  \w     16.00 118.00   0.50    0.50    --   48.00  77.00-167.85  204
  6  \w     16.00  59.00   0.50    0.50    --   52.00  79.00 -90.53   86
  7  \w     88.00 131.00   0.50    0.50    --   52.00  79.00 -90.53   86
  8  \w     19.00  45.00   0.50    0.50    --   56.00  82.00 -24.67   52
  9  \w     27.00  52.00   0.50    0.50    --   56.00  74.00 130.75   50
 10  \w     95.00 145.00   0.50    0.50    --   56.00  74.00 130.75  100
 11  \w     24.00  50.00   0.50    0.50    --   60.00  80.00  35.10   52
 12  \w     32.00  58.00   0.50    0.50    --   68.00  82.00-119.78   52
 13  \w     33.00  67.00   0.50    0.50    --   68.00  82.00 128.09   68
 14  \w     31.00 105.00   0.50    0.50    --   68.00  80.00  70.41  148
 15  \w     31.00  57.00   0.50    0.50    --   68.00  82.00 -15.51   52
 16  \w    130.00 161.00   0.50    0.50    --   76.00  81.00 -68.60   62
 17  \w     39.00  91.00   0.50    0.50    --   76.00  81.00 -68.60  104
 18  \w     39.00  71.00   0.50    0.50    --   76.00  81.00 157.20   64
 19  \w    114.00 167.00   0.50    0.50    --   80.00  73.00  42.15  106
 20  \w     93.00 147.00   0.50    0.50    --   80.00  81.00-116.10  108
 21  \w     47.00  81.00   0.50    0.50    --   80.00  73.00  42.15   68
 22  \w     43.00  69.00   0.50    0.50    --   80.00  82.00 -15.52   52
 23  \w     47.00  73.00   0.50    0.50    --   80.00  81.00-116.10   52
 24  \w     47.00 137.00   0.50    0.50    --   84.00  82.00-173.82  180
 25  \w    139.00 171.00   0.50    0.50    --   97.60  82.00 -60.00   64
 26  \w     60.00 135.00   0.50    0.50    --   97.60  82.00 -60.00  150
 27  \w     48.00 132.00   0.50    0.50    --   97.60 -82.00-120.00  168
 28  \w    148.00 187.00   0.50    0.50    --   97.60  82.00 -30.00   78
 29  \w     63.00  88.00   0.50    0.50    --   97.60  82.00  30.00   50
 30  \w    107.00 150.00   0.50    0.50    --   97.60  82.00  30.00   86
 31  \w     61.00 145.00   0.50    0.50    --   97.60  82.00 -30.00  168
 32  \w     61.00 118.00   0.50    0.50    --   97.60  82.00  60.00  114
 33  \w     10.00 127.00   0.50    0.50    --   97.60 -61.00  30.00  234
 34  \w     67.00 187.00   0.50    0.50    --   97.60  64.00 134.49  240
 35  \w      9.00  34.00   0.50    0.50    --   97.60 -82.00 120.00   50
 36  \w     47.00 130.00   0.50    0.50    --   97.60 -82.00  30.00  166
 37  \w     70.00 187.00   0.50    0.50    --   97.60  45.00 -60.00  234
 38  \w    103.00 128.00   0.50    0.50    --   97.60  77.00 150.00   50
 39  \w     62.00  98.00   0.50    0.50    --   97.60  77.00 150.00   72
 40  \w     98.00 171.00   0.50    0.50    --   97.60  45.00 120.00  146
 41  \w     60.00 116.00   0.50    0.50    --   97.60  82.00-150.00  112
 42  \w    121.00 153.00   0.50    0.50    --   97.60  82.00-150.00   64
 43  \w     17.00  42.00   0.50    0.50    --   97.60 -82.00  30.00   50
 44  \w     79.00 134.00   0.50    0.50    --   97.60 -82.00 120.00  110
 45  \w     58.00 110.00   0.50    0.50    --   97.60 -82.00 -60.00  104
 46  \w     66.00 182.00   0.50    0.50    --   97.60  78.00 -10.17  232
 47  \w    137.00 174.00   0.50    0.50    --   97.60  77.00  90.00   74
 48  \w     83.00 183.00   0.50    0.50    --   97.60  61.00-120.00  200
 49  \w     81.00 178.00   0.50    0.50    --   97.60  61.00  60.00  194
 50  \w     64.00 123.00   0.50    0.50    --   97.60  77.00  90.00  118
 51  \w    111.00 137.00   0.50    0.50    --   97.60  77.00-180.00   52
 52  \w     64.00  91.00   0.50    0.50    --   97.60  77.00-180.00   54
 53  \w    162.00 187.00   0.50    0.50    --   97.60  82.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0143418000
_diffrn_orient_matrix_UB_12      0.0273469000
_diffrn_orient_matrix_UB_13      0.1058138000
_diffrn_orient_matrix_UB_21      -0.1054908000
_diffrn_orient_matrix_UB_22      0.1091793000
_diffrn_orient_matrix_UB_23      -0.0298526000
_diffrn_orient_matrix_UB_31      -0.0642209000
_diffrn_orient_matrix_UB_32      -0.1730839000
_diffrn_orient_matrix_UB_33      -0.0021015000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0180
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            28817
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.315
_diffrn_reflns_theta_min         3.153
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.521
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61574
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
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    1.178
_exptl_crystal_description       plate
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.149
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2380 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.28(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         5434
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0344
_refine_ls_R_factor_gt           0.0341
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0626P)^2^+0.1623P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0918
_refine_ls_wR_factor_ref         0.0921
_reflns_Friedel_coverage         0.823
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                5346
_reflns_number_total             5434
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02338_si_001.cif
_cod_data_source_block           20190128a1
_cod_database_code               4128666
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.803
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C15(H15), C33(H33)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C29(H29),
  C30(H30)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              61315
_shelx_hkl_checksum              49654
_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 1.653
_oxdiff_exptl_absorpt_empirical_full_min 0.580