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_4134157
_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         'C27 H19 N'
_chemical_formula_sum            'C27 H19 N'
_chemical_formula_weight         357.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-09-17
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.778(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.1558(4)
_cell_length_b                   5.68250(13)
_cell_length_c                   18.9738(4)
_cell_measurement_reflns_used    3238
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.7230
_cell_measurement_theta_min      4.7600
_cell_volume                     1810.77(7)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.976
_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    -74.00   8.60   0.70    0.50    --  -46.75  93.00 137.00  118
  2  \w     45.00  71.60   0.70    0.50    --   46.75 -93.00  25.00   38
  3  \w    -15.00  10.20   0.70    0.50    --   46.75 -93.00  25.00   36
  4  \w    -82.00 -36.50   0.70    1.07    --  -88.50  93.00 137.00   65
  5  \w     57.00 108.10   0.70    1.07    --  110.00 -93.00  25.00   73
  6  \w    108.00 171.00   0.70    1.07    --  110.00  93.00 137.00   90
  7  \w   -118.00 -70.40   0.70    0.50    --  -46.75-125.00-180.00   68
  8  \w    -50.00  26.30   0.70    0.50    --  -46.75  37.00  30.00  109
  9  \w   -151.00-123.70   0.70    1.07    --  -88.50 -37.00  60.00   39
 10  \w   -149.00 -95.80   0.70    1.07    --  -88.50 -93.00  25.00   76
 11  \w   -116.00 -74.00   0.70    1.07    --  -88.50 -57.00 -60.00   60
 12  \w   -162.00-120.70   0.70    1.07    --  -88.50 -19.00  90.00   59
;
_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      0.0034612000
_diffrn_orient_matrix_UB_12      0.0375990000
_diffrn_orient_matrix_UB_13      0.0809888000
_diffrn_orient_matrix_UB_21      -0.0356042000
_diffrn_orient_matrix_UB_22      0.2480736000
_diffrn_orient_matrix_UB_23      -0.0157385000
_diffrn_orient_matrix_UB_31      -0.0844403000
_diffrn_orient_matrix_UB_32      -0.1030696000
_diffrn_orient_matrix_UB_33      -0.0084290000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            10277
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.058
_diffrn_reflns_theta_min         4.762
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.577
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82945
_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    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.592
_refine_diff_density_min         -0.280
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3204
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0558
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0514P)^2^+1.2408P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1267
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2747
_reflns_number_total             3204
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13975_si_005.cif
_cod_data_source_block           wzs-20180917-1
_cod_database_code               4134157
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C H N'
_diffrn_oxdiff_ac3_digest_frames
;
018b587dc48fbf63bd243c56d21b8385ea00041cbf6
;
_diffrn_oxdiff_ac3_digest_hkl    0142d1b0ceae2dbb8055fa2c6fe757e54bd4bb
_reflns_odcompleteness_completeness 85.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C26(H26)
;
_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 1.199
_oxdiff_exptl_absorpt_empirical_full_min 0.683