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_4134154
_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 H20 F3 N'
_chemical_formula_sum            'C29 H20 F3 N'
_chemical_formula_weight         439.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3590(2)
_cell_length_b                   9.3701(2)
_cell_length_c                   17.1113(3)
_cell_measurement_reflns_used    2911
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      68.4210
_cell_measurement_theta_min      4.1970
_cell_volume                     2141.91(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.977
_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    -61.00  35.00   1.00    1.00    --  -40.88  37.00 -60.00   96
  2  \w     22.00  63.00   1.00    1.00    --   40.88 -77.00-120.00   41
  3  \w     20.00  99.00   1.00    2.50    --   97.12 -94.00 150.00   79
  4  \w     99.00 153.00   1.00    2.50    --   97.12 125.00 150.00   54
  5  \w     27.00 125.00   1.00    2.50    --   97.12 -30.00-120.00   98
  6  \w    129.00 155.00   1.00    2.50    --   97.12 125.00   0.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0168438000
_diffrn_orient_matrix_UB_12      0.1468480000
_diffrn_orient_matrix_UB_13      -0.0383986000
_diffrn_orient_matrix_UB_21      0.0109217000
_diffrn_orient_matrix_UB_22      0.0725798000
_diffrn_orient_matrix_UB_23      0.0803811000
_diffrn_orient_matrix_UB_31      0.1134794000
_diffrn_orient_matrix_UB_32      0.0145838000
_diffrn_orient_matrix_UB_33      -0.0133111000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            4806
_diffrn_reflns_point_group_measured_fraction_full 0.690
_diffrn_reflns_point_group_measured_fraction_max 0.684
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.287
_diffrn_reflns_theta_min         4.719
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.801
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68826
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (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    1.363
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.289
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 650 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.54(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         2694
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0840P)^2^+0.0845P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1140
_refine_ls_wR_factor_ref         0.1165
_reflns_Friedel_coverage         0.348
_reflns_Friedel_fraction_full    0.372
_reflns_Friedel_fraction_max     0.367
_reflns_number_gt                2597
_reflns_number_total             2694
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13975_si_004.cif
_cod_data_source_block           exp_9416
_cod_database_code               4134154
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     63.60
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B)
2.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C29(H29), C3(H3), C18(H18), C6(H6), C19(H19), C15(H15), C11(H11),
 C8(H8), C28(H28), C1(H1), C2(H2), C26(H26), C9(H9), C27(H27), C10(H10),
 C16(H16), C17(H17)
;
_shelx_res_checksum              19175
_shelx_hkl_checksum              34468
_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 1.515
_oxdiff_exptl_absorpt_empirical_full_min 0.690