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_4134152
_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 H21 N'
_chemical_formula_sum            'C29 H21 N'
_chemical_formula_weight         383.47
_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             2018-12-10
_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                 98.357(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.9018(3)
_cell_length_b                   9.3208(3)
_cell_length_c                   10.9888(4)
_cell_measurement_reflns_used    2822
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.8390
_cell_measurement_theta_min      4.0500
_cell_volume                     1003.42(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.21a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a (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 0.983
_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    -78.00 -32.64   0.84    0.10    --  -46.75 105.00 -31.00   54
  2  \w    -20.00   5.20   0.84    0.10    --  -46.75 105.00 -31.00   30
  3  \w     16.00  63.04   0.84    0.10    --   46.75-105.00-131.00   56
  4  \w    -71.00 -29.84   0.84    0.39    --  -88.50 105.00 -31.00   49
  5  \w   -137.00-112.64   0.84    0.39    --  -88.50-105.00-131.00   29
  6  \w     66.00 110.52   0.84    0.39    --  107.31-105.00-131.00   53
  7  \w   -119.00 -73.64   0.84    0.10    --  -46.75-125.00  30.00   54
  8  \w   -119.00 -77.84   0.84    0.10    --  -46.75-125.00 -60.00   49
  9  \w     -6.00  61.20   0.84    0.10    --   46.75 -37.00 -60.00   80
 10  \w   -104.00 -73.76   0.84    0.39    --  -88.50 -30.00 -90.00   36
 11  \w   -161.00 -98.00   0.84    0.39    --  -88.50 -45.00-120.00   75
 12  \w   -163.00-112.60   0.84    0.39    --  -88.50 -30.00 -90.00   60
 13  \w     67.00 101.44   0.84    0.39    --  107.31 -94.00 -90.00   41
 14  \w    100.00 126.04   0.84    0.39    --  107.31 -77.00-120.00   31
 15  \w     35.00  78.68   0.84    0.39    --  107.31 -77.00-120.00   52
 16  \w    133.00 177.52   0.84    0.39    --  107.31  15.00 150.00   53
 17  \w     35.00 104.72   0.84    0.39    --  107.31 -94.00  60.00   83
 18  \w     94.00 119.20   0.84    0.39    --  107.31  15.00 150.00   30
 19  \w     95.00 121.04   0.84    0.39    --  107.31  45.00-120.00   31
 20  \w    141.00 170.40   0.84    0.39    --  107.31  45.00-120.00   35
 21  \w    105.00 164.64   0.84    0.39    --  107.31 105.00 -31.00   71
;
_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      -0.1356948000
_diffrn_orient_matrix_UB_12      -0.0237300000
_diffrn_orient_matrix_UB_13      0.0502342000
_diffrn_orient_matrix_UB_21      0.0013452000
_diffrn_orient_matrix_UB_22      0.1577209000
_diffrn_orient_matrix_UB_23      0.0421384000
_diffrn_orient_matrix_UB_31      -0.0793380000
_diffrn_orient_matrix_UB_32      0.0433132000
_diffrn_orient_matrix_UB_33      -0.1256576000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0618
_diffrn_reflns_av_unetI/netI     0.0668
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6059
_diffrn_reflns_point_group_measured_fraction_full 0.825
_diffrn_reflns_point_group_measured_fraction_max 0.840
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.066
_diffrn_reflns_theta_min         4.066
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.557
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68631
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.21a (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    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             404
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 894 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.4(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.271
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         3001
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.270
_refine_ls_R_factor_all          0.0620
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0802P)^2^+0.4235P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1748
_refine_ls_wR_factor_ref         0.1867
_reflns_Friedel_coverage         0.574
_reflns_Friedel_fraction_full    0.645
_reflns_Friedel_fraction_max     0.656
_reflns_number_gt                2674
_reflns_number_total             3001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13975_si_006.cif
_cod_data_source_block           wzs-20181210
_cod_original_cell_volume        1003.42(5)
_cod_database_code               4134152
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.946
_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, All N(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B)
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), C23(H23), C25(H25), C26(H26),
  C27(H27), C28(H28), C29(H29)
;
_shelx_res_checksum              60564
_shelx_hkl_checksum              9829
_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 1.360
_oxdiff_exptl_absorpt_empirical_full_min 0.703