Metal-free radical cascade cyclization/haloazidation of enynones to access functionalized 1-indanones.
Yan, Hua-Feng; Zou, Xiao; Wang, Jian-Qiang; Guo, Cheng; Zuo, Hang-Dong; Organic & biomolecular chemistry 23 (2025) 1067–1072; doi:10.1039/d4ob01810a

data_7160295
_publ_section_title
;
 Metal-free radical cascade cyclization/haloazidation of enynones to
 access functionalized 1-indanones.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1067
_journal_page_last               1072
_journal_paper_doi               10.1039/d4ob01810a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         '0.5(C36 H28 I2 N6 O2)'
_chemical_formula_sum            'C18 H14 I N3 O'
_chemical_formula_weight         415.22
_space_group_crystal_system      orthorhombic
_space_group_IT_number           72
_space_group_name_Hall           '-I 2 2c'
_space_group_name_H-M_alt        'I b a m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-13 deposited with the CCDC.	2024-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.5176(3)
_cell_length_b                   42.1854(13)
_cell_length_c                   7.4578(2)
_cell_measurement_reflns_used    4248
_cell_measurement_temperature    100.1(7)
_cell_measurement_theta_max      75.5640
_cell_measurement_theta_min      4.2020
_cell_volume                     3308.95(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.1(7)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.933
_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     36.00  62.00   0.50    0.20    --  106.86 -61.00 150.00   52
  2  \w     39.00  65.00   0.50    0.20    --  106.86 -61.00  90.00   52
  3  \w     38.00  67.00   0.50    0.20    --  106.86 -61.00  60.00   58
  4  \w     52.00  81.00   0.50    0.20    --  106.86 -69.00  25.00   58
  5  \w     37.00  65.00   0.50    0.20    --  106.86 -61.00-180.00   56
  6  \w    -21.00  23.00   0.50    0.05    --   46.46 -19.00-120.00   88
  7  \w   -168.00 -80.00   0.50    0.20    --  -97.00 -54.00-137.00  176
  8  \w   -123.00 -92.00   0.50    0.20    --  -97.00-111.00 143.00   62
  9  \w   -156.00-130.00   0.50    0.20    --  -97.00-111.00 143.00   52
 10  \w    -29.00  -4.00   0.50    0.05    --   46.46 -19.00 120.00   50
 11  \w     39.00 109.00   0.50    0.05    --   46.46  69.00 157.00  140
 12  \w     34.00  96.00   0.50    0.20    --  106.86 -95.00-150.00  124
 13  \w    -29.00  25.00   0.50    0.05    --  -46.46  19.00-180.00  108
 14  \w    -54.00 -29.00   0.50    0.20    --  -97.00  45.00-150.00   50
 15  \w    -51.00 -25.00   0.50    0.20    --  -97.00  45.00  60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0563501000
_diffrn_orient_matrix_UB_12      0.0030989000
_diffrn_orient_matrix_UB_13      -0.0351374000
_diffrn_orient_matrix_UB_21      -0.1227182000
_diffrn_orient_matrix_UB_22      -0.1146509000
_diffrn_orient_matrix_UB_23      -0.0068039000
_diffrn_orient_matrix_UB_31      -0.1561677000
_diffrn_orient_matrix_UB_32      0.0910238000
_diffrn_orient_matrix_UB_33      -0.0073206000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            5878
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.077
_diffrn_reflns_theta_min         4.192
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    15.268
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67344
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.667
_exptl_crystal_description       block
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.937
_refine_diff_density_min         -0.851
_refine_diff_density_rms         0.186
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         1752
_refine_ls_number_restraints     150
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0787
_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^)+(0.0748P)^2^+89.9998P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2101
_refine_ls_wR_factor_ref         0.2113
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1611
_reflns_number_total             1752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01810a2.cif
_cod_data_source_block           a
_cod_depositor_comments          'Adding full bibliography for 7160295.cif.'
_cod_database_code               7160295
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.340
_shelx_estimated_absorpt_t_min   0.262
_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
2. Uiso/Uaniso restraints and constraints
C11 \\sim I1 \\sim C7 \\sim C6 \\sim C8 \\sim C1 \\sim C5 \\sim C16 \\sim C9
\\sim C2 \\sim C4 \\sim C15 \\sim C17 \\sim C18 \\sim O1 \\sim C10 \\sim C3
\\sim C14 \\sim N1 \\sim C13 \\sim N2 \\sim C12 \\sim N3: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: N2(0.5) O1(0.5) N1(0.5) C16(0.5) C1(0.5) H1(0.5) C6(0.5) C5(0.5)
 H5(0.5) C4(0.5) H4(0.5) C3(0.5) H3(0.5) C2(0.5) H2(0.5) C15(0.5) C10(0.5)
 C11(0.5) H11(0.5) C12(0.5) H12(0.5) C13(0.5) H13(0.5) C14(0.5) H14(0.5)
 C9(0.5) C8(0.5) C7(0.5) N3(0.5) C17(0.5) H17A(0.5) H17B(0.5) H17C(0.5)
 C18(0.5) H18A(0.5) H18B(0.5)
 Fixed Z: N2(0.997009) C16(0.996799)
4.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C4(H4), C3(H3), C2(H2), C11(H11), C12(H12), C13(H13), C14(H14)
4.c Fitted hexagon refined as free rotating group:
 C1(C6,C5,C4,C3,C2), C15(C10,C11,C12,C13,C14)
4.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_shelx_res_checksum              88553
_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 2.945
_oxdiff_exptl_absorpt_empirical_full_min 0.549