Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines.
Wang, Ze-Shu; Chen, Yang-Bo; Zhang, Hao-Wen; Sun, Zhou; Zhu, Chunyin; Ye, Long-Wu; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b13975

data_4134155
_publ_section_title
;
 Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated
 Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized
 Indoles and Isoquinolines.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b13975
_journal_year                    2020
_chemical_formula_moiety         'C29 H19 N'
_chemical_formula_sum            'C29 H19 N'
_chemical_formula_weight         381.45
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-17
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.2464(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.52164(10)
_cell_length_b                   18.4767(2)
_cell_length_c                   12.06929(12)
_cell_measurement_reflns_used    7244
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.5230
_cell_measurement_theta_min      4.3820
_cell_volume                     1892.37(4)
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 1.000
_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    -80.00 -16.00   0.50    0.05    --  -46.75  98.00  53.00  128
  2  \w     41.00  68.00   0.50    0.05    --   46.75 -98.00 -54.00   54
  3  \w      2.00  29.00   0.50    0.05    --   46.75 -98.00 -54.00   54
  4  \w    -73.00 -48.00   0.50    0.18    --  -88.50  98.00  53.00   50
  5  \w     48.00  99.00   0.50    0.18    --  110.00 -98.00 -54.00  102
  6  \w    108.00 157.00   0.50    0.18    --  110.00  98.00  53.00   98
  7  \w   -114.00 -70.00   0.50    0.05    --  -46.75-125.00  90.00   88
  8  \w    -61.00  27.00   0.50    0.05    --  -46.75  37.00 -60.00  176
  9  \w   -114.00 -81.00   0.50    0.05    --  -46.75-125.00  30.00   66
 10  \w   -118.00 -82.00   0.50    0.05    --  -46.75-125.00-180.00   72
 11  \w   -117.00 -92.00   0.50    0.18    --  -88.50 -57.00   0.00   50
 12  \w   -154.00-124.00   0.50    0.18    --  -88.50 -57.00   0.00   60
 13  \w   -158.00 -95.00   0.50    0.18    --  -88.50 -98.00 -54.00  126
 14  \w     46.00 106.00   0.50    0.18    --  110.00 -99.00  60.00  120
 15  \w     39.00  92.00   0.50    0.18    --  110.00 -99.00-120.00  106
 16  \w     96.00 156.00   0.50    0.18    --  110.00 125.00   0.00  120
 17  \w     40.00  95.00   0.50    0.18    --  110.00 -37.00  60.00  110
 18  \w     39.00 109.00   0.50    0.18    --  110.00 -99.00-180.00  140
 19  \w     75.00 100.00   0.50    0.18    --  110.00 -99.00 -30.00   50
 20  \w     98.00 175.00   0.50    0.18    --  110.00  57.00-180.00  154
;
_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      0.0181804000
_diffrn_orient_matrix_UB_12      0.0786634000
_diffrn_orient_matrix_UB_13      0.0415346000
_diffrn_orient_matrix_UB_21      -0.1714931000
_diffrn_orient_matrix_UB_22      -0.0008340000
_diffrn_orient_matrix_UB_23      0.0308298000
_diffrn_orient_matrix_UB_31      0.0566738000
_diffrn_orient_matrix_UB_32      -0.0276354000
_diffrn_orient_matrix_UB_33      0.1172809000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            11636
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         4.389
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.590
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40071
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         3388
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0498
_refine_ls_R_factor_gt           0.0429
_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^)+(0.0675P)^2^+0.6578P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1131
_refine_ls_wR_factor_ref         0.1221
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3028
_reflns_number_total             3388
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13975_si_007.cif
_cod_data_source_block           wzs-20181217
_cod_database_code               4134155
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.943
_reflns_odcompleteness_completeness 99.94
_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 N(H) groups
2.a Ternary CH refined with riding coordinates:
 C23(H23)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C13(H13), C14(H14), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29)
;
_shelx_res_checksum              13746
_shelx_hkl_checksum              29023
_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 1.759
_oxdiff_exptl_absorpt_empirical_full_min 0.478