Atom-economical and workup-free multiparticipation of p-TsOH in yne-ynamide skeletal reshuffle: access to regiospecific, chemospecific, and stereospecific (E)-alkenyl sulfonate/ketone-tethered indoles
Mutra, Mohana Reddy; Chandana, T. L.; Wang, Jeh-Jeng; Green Chemistry 27 (2025) 1062–1072; doi:10.1039/D4GC05876C

data_7249695
_publ_section_title
;
 Atom-economical and workup-free multiparticipation of p-TsOH in
 yne-ynamide skeletal reshuffle: access to regiospecific, chemospecific,
 and stereospecific (E)-alkenyl sulfonate/ketone-tethered indoles
;
_journal_issue                   4
_journal_name_full               'Green Chemistry'
_journal_page_first              1062
_journal_page_last               1072
_journal_paper_doi               10.1039/D4GC05876C
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C36 H29 N O5 S2'
_chemical_formula_sum            'C36 H29 N O5 S2'
_chemical_formula_weight         619.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-13 deposited with the CCDC.	2024-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                87.3880(10)
_cell_angle_beta                 78.3450(10)
_cell_angle_gamma                75.5430(10)
_cell_formula_units_Z            2
_cell_length_a                   10.0336(2)
_cell_length_b                   11.9429(2)
_cell_length_c                   13.2152(2)
_cell_measurement_reflns_used    41023
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      27.0340
_cell_measurement_theta_min      1.7470
_cell_volume                     1501.80(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      130(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.938
_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    -14.00 100.00   0.50    5.04    --   10.60  65.00-101.00  228
  2  \w    -79.00  35.00   0.50    5.04    --   10.60 -65.00 123.00  228
  3  \w    -35.00  78.00   0.50    5.04    --  -10.90  65.00-101.00  226
  4  \w   -100.00  13.00   0.50    5.04    --  -10.90 -65.00 123.00  226
  5  \w    -79.00  41.00   0.50    5.04    --   10.60 -57.00-180.00  240
  6  \w    -15.00 100.00   0.50    5.04    --   10.60  77.00 150.00  230
  7  \w    -17.00 100.00   0.50    5.04    --   10.60  82.00  90.00  234
  8  \w    -17.00 100.00   0.50    5.04    --   10.60  82.00-150.00  234
  9  \w    -79.00  36.00   0.50    5.04    --   10.60 -77.00-180.00  230
 10  \w    -17.00 100.00   0.50    5.04    --   10.60  82.00  60.00  234
 11  \w    -15.00 100.00   0.50    5.04    --   10.60  77.00   0.00  230
 12  \w    -17.00 100.00   0.50    5.04    --   10.60  82.00   0.00  234
 13  \w    -17.00 100.00   0.50    5.04    --   10.60  82.00 -90.00  234
 14  \w    -48.00  79.00   0.50    5.04    --  -10.90  37.00-150.00  254
 15  \w    -36.00  79.00   0.50    5.04    --  -10.90  77.00 -60.00  230
 16  \w   -100.00  17.00   0.50    5.04    --  -10.90 -82.00  60.00  234
 17  \w   -100.00  17.00   0.50    5.04    --  -10.90 -82.00-150.00  234
 18  \w    -36.00  79.00   0.50    5.04    --  -10.90  77.00  30.00  230
 19  \w    -79.00 -51.00   0.50    5.04    --   10.60 -82.00 120.00   56
 20  \w    -79.00  38.00   0.50    5.04    --   10.60 -82.00  60.00  234
 21  \w    -79.00  38.00   0.50    5.04    --   10.60 -82.00  90.00  234
 22  \w    -38.00  79.00   0.50    5.04    --  -10.90  82.00 -90.00  234
 23  \w    -38.00  79.00   0.50    5.04    --  -10.90  82.00 -30.00  234
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II 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      -0.0139261000
_diffrn_orient_matrix_UB_12      -0.0388178000
_diffrn_orient_matrix_UB_13      0.0407089000
_diffrn_orient_matrix_UB_21      0.0701810000
_diffrn_orient_matrix_UB_22      -0.0100534000
_diffrn_orient_matrix_UB_23      0.0071943000
_diffrn_orient_matrix_UB_31      -0.0206305000
_diffrn_orient_matrix_UB_32      0.0464105000
_diffrn_orient_matrix_UB_33      0.0359790000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0634
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            66920
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.346
_diffrn_reflns_theta_min         1.573
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.223
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81547
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.370
_exptl_crystal_description       block
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.410
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         6361
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0464P)^2^+0.5647P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.1010
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5508
_reflns_number_total             6361
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc05876c2.cif
_cod_data_source_block           k11301-jjw-a_auto
_cod_depositor_comments
'Adding full bibliography for 7249694--7249695.cif.'
_cod_database_code               7249695
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.896
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C7(H7), C4(H4), C31(H31), C5(H5), C14(H14), C16(H16), C6(H6),
 C18(H18), C13(H13), C24(H24), C28(H28), C27(H27), C11(H11), C12(H12), C25(H25),
  C32(H32), C35(H35), C22(H22), C34(H34), C19(H19), C20(H20), C21(H21)
2.b Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              10700
_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 2.233
_oxdiff_exptl_absorpt_empirical_full_min 0.654