<i>L</i>-region-selective annulative π-extension through dearomative activation of polycyclic aromatic hydrocarbons.
Nakata, Kanami; Matsuoka, Wataru; Ito, Hideto; Itami, Kenichiro; Chemical science 17 (2026) 3998–4003; doi:10.1039/d5sc09309k

data_1576663
_publ_section_title
;
 <i>L</i>-region-selective annulative &#x3c0;-extension through
 dearomative activation of polycyclic aromatic hydrocarbons.
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              3998
_journal_page_last               4003
_journal_paper_doi               10.1039/d5sc09309k
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C25.04 H20.04 I N3 O2'
_chemical_formula_sum            'C25.04 H20.04 I N3 O2'
_chemical_formula_weight         521.86
_chemical_name_systematic        'compound 8'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-25
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.05 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5625)
;
_audit_update_record
;
2025-11-27 deposited with the CCDC.	2026-01-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.325(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3604(10)
_cell_length_b                   9.5211(7)
_cell_length_c                   15.3873(10)
_cell_measurement_reflns_used    6713
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      29.7690
_cell_measurement_theta_min      2.5520
_cell_volume                     2148.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_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      123(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.773
_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    -16.00  21.00   0.50    1.91    --    3.32 -62.00 164.00   74
  2  \w    -42.00  20.00   0.50    1.91    --   -2.70 -90.00  61.00  124
  3  \w    -20.00  13.00   0.50    1.91    --   -2.70 -57.00-120.00   66
  4  \w    -68.00 -33.00   0.50    1.91    --   -2.70 -57.00-120.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0183347000
_diffrn_orient_matrix_UB_12      -0.0329024000
_diffrn_orient_matrix_UB_13      -0.0430451000
_diffrn_orient_matrix_UB_21      0.0118239000
_diffrn_orient_matrix_UB_22      0.0596553000
_diffrn_orient_matrix_UB_23      -0.0216261000
_diffrn_orient_matrix_UB_31      0.0431161000
_diffrn_orient_matrix_UB_32      -0.0302259000
_diffrn_orient_matrix_UB_33      0.0037589000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0616
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.773
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            11670
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.773
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         29.832
_diffrn_reflns_theta_min         2.549
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.518
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84256
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale yellow'
_exptl_crystal_density_diffrn    1.614
_exptl_crystal_description       block
_exptl_crystal_F_000             1041
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: EtOAc/hexane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.744
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.176
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     346
_refine_ls_number_reflns         4771
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.0711
_refine_ls_R_factor_gt           0.0566
_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^)+9.5741P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1270
_refine_ls_wR_factor_ref         0.1307
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3803
_reflns_number_total             4771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09309k2.cif
_cod_data_source_block           knm309d_etoac_hexane_x-ray_auto
_cod_database_code               1576663
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N O I H'
_shelx_estimated_absorpt_t_max   0.804
_shelx_estimated_absorpt_t_min   0.751
_diffrn_oxdiff_digest_frames
;
016292a47c11436f2809e437f24419183800026855d
;
_diffrn_oxdiff_digest_hkl
;
01e4750afd15e599cc9bee88f71dfbc660b347
;
_reflns_odcompleteness_completeness 97.33
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C25-C26 = C29-C28 = C28-C27 = C27-C26
 1.4 with sigma of 0.01
 C26-C28
 2.4 with sigma of 0.01
 C27-C29
 2.4 with sigma of 0.01
 C29-C25
 2.4 with sigma of 0.01
 C25-C27
 2.4 with sigma of 0.01
 C37-C32 = C37-C36 = C35-C36 = C34-C35 = C33-C34 = C33-C32
 1.4 with sigma of 0.01
 C32-C36
 2.4 with sigma of 0.01
 C37-C35
 2.4 with sigma of 0.01
 C36-C34
 2.4 with sigma of 0.01
 C35-C33
 2.4 with sigma of 0.01
 C34-C32
 2.4 with sigma of 0.01
 C33-C37
 2.4 with sigma of 0.01
3. Restrained planarity
 C34, C33, I38, C32, C37, C36, C35
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.01
Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.01
5. Others
 Sof(C32)=Sof(C36)=Sof(H00W)=Sof(C35)=Sof(H1AA)=Sof(C34)=Sof(H2AA)=Sof(C33)=
 Sof(I38)=1-FVAR(1)
 Sof(I31)=Sof(C26)=Sof(C27)=Sof(H00S)=Sof(C25)=Sof(C28)=Sof(H00U)=Sof(C29)=
 Sof(H00V)=Sof(C30)=Sof(H1)=FVAR(1)
 Sof(C37)=Sof(H1A)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H00C), C4(H00O)
6.b Aromatic/amide H refined with riding coordinates:
 N12(H007), C3(H00D), C6(H00E), C2(H00F), C7(H00G), C9(H00I), C22(H00J),
 C24(H00K), C23(H00N), C8(H00P), C21(H00Q), C27(H00S), C28(H00U), C29(H00V),
 C30(H1), C37(H1A), C36(H00W), C35(H1AA), C34(H2AA)
6.c Idealised Me refined as rotating group:
 C17(H00A,H00B,H00H)
;
_shelx_res_checksum              70782
_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 1.301
_oxdiff_exptl_absorpt_empirical_full_min 0.805