Macrocyclization <i>via</i> remote <i>meta</i>-selective C-H olefination using a practical indolyl template.
Zhang, Pengfei; Jiang, Zhiwei; Fan, Zhoulong; Li, Guoshuai; Ma, Qingxue; Huang, Jun; Tang, Jinghong; Xu, Xiaohua; Yu, Jin-Quan; Jin, Zhong; Chemical science 14 (2023) 8279–8287; doi:10.1039/d3sc01670f

data_1569480
_publ_section_title
;
 Macrocyclization <i>via</i> remote <i>meta</i>-selective C-H olefination
 using a practical indolyl template.
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              8279
_journal_page_last               8287
_journal_paper_doi               10.1039/d3sc01670f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C29 H26 N2 O4 S, 0.5(C H4 O)'
_chemical_formula_sum            'C29.5 H28 N2 O4.5 S'
_chemical_formula_weight         514.60
_chemical_melting_point          122-123?
_chemical_name_systematic
'ethyl (E)-3-(3-((3-(2-cyanophenyl)-2,5-dimethyl-1H-indol-1-yl)sulfonyl)-5-methylphenyl)acrylate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-17 deposited with the CCDC.	2023-07-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.759(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.8311(11)
_cell_length_b                   8.2255(4)
_cell_length_c                   29.1754(14)
_cell_measurement_reflns_used    8257
_cell_measurement_temperature    113.15
_cell_measurement_theta_max      33.6520
_cell_measurement_theta_min      2.2390
_cell_volume                     5227.8(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_temperature      113.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.939
_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   -120.00  60.00   1.00    2.00    --  -30.00  45.00   0.00  180
  2  \w   -120.00  60.00   1.00    2.00    --  -30.00  45.00  90.00  180
  3  \w   -120.00  60.00   1.00    2.00    --  -30.00  45.00 180.00  180
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Saturn 70 CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0099897000
_diffrn_orient_matrix_UB_12      -0.0116065000
_diffrn_orient_matrix_UB_13      -0.0224089000
_diffrn_orient_matrix_UB_21      0.0309695000
_diffrn_orient_matrix_UB_22      0.0009090000
_diffrn_orient_matrix_UB_23      0.0090149000
_diffrn_orient_matrix_UB_31      -0.0010270000
_diffrn_orient_matrix_UB_32      -0.0854715000
_diffrn_orient_matrix_UB_33      0.0031477000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0976
_diffrn_reflns_av_unetI/netI     0.1001
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            37167
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.574
_diffrn_reflns_theta_min         1.870
_diffrn_source                   'rotating anode'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.164
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47224
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_exptl_crystal_colour            White
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_description       block
_exptl_crystal_F_000             2168
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Methanol'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.609
_refine_diff_density_min         -0.580
_refine_diff_density_rms         0.079
_refine_ls_extinction_coef       0.00121(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     350
_refine_ls_number_reflns         9693
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1549
_refine_ls_R_factor_gt           0.0815
_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^)+(0.0614P)^2^+6.9684P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1636
_refine_ls_wR_factor_ref         0.2054
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5247
_reflns_number_total             9693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01670f2.cif
_cod_data_source_block           r20210514d
_cod_depositor_comments          'Adding full bibliography for 1569480.cif.'
_cod_original_formula_sum        'C29.50 H28 N2 O4.50 S'
_cod_database_code               1569480
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.963
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O5-C30
 1.45 with sigma of 0.01
3. Others
 Fixed Sof: O5(0.5) H5A(0.5) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C9(H9), C11(H11), C16(H16), C17(H17), C19(H19),
 C24(H24), C25(H25), C26(H26), C27(H27)
4.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C22(H22A,H22B,
 H22C), C30(H30A,H30B,H30C)
4.d Idealised tetrahedral OH refined as rotating group:
 O5(H5A)
;
_shelx_res_checksum              20728
_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 2.435
_oxdiff_exptl_absorpt_empirical_full_min 0.652