<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_1576662
_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 H21 N3 O2'
_chemical_formula_sum            'C25 H21 N3 O2'
_chemical_formula_weight         395.45
_chemical_name_systematic        'compound 5'
_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             2021-10-14
_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                 104.524(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9010(14)
_cell_length_b                   10.1314(7)
_cell_length_c                   13.5202(11)
_cell_measurement_reflns_used    4080
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      27.8580
_cell_measurement_theta_min      2.4420
_cell_volume                     1975.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_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                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.832
_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    -71.00  92.00   0.50  140.00    --    8.30   9.00 -75.00  326
  2  \w     13.00  39.00   0.50  140.00    --   -7.75  37.00-180.00   52
  3  \w    -23.00   8.00   0.50  140.00    --   -7.75  37.00-180.00   62
  4  \w    -13.00  39.00   0.50  140.00    --   -7.75 -99.00  30.00  104
  5  \w    -15.00  22.00   0.50  140.00    --    8.30 -99.00  90.00   74
  6  \w     67.00  92.00   0.50  140.00    --    8.30 179.00  60.00   50
;
_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      0.0116729000
_diffrn_orient_matrix_UB_12      -0.0079311000
_diffrn_orient_matrix_UB_13      -0.0473961000
_diffrn_orient_matrix_UB_21      0.0476666000
_diffrn_orient_matrix_UB_22      -0.0021685000
_diffrn_orient_matrix_UB_23      0.0258873000
_diffrn_orient_matrix_UB_31      -0.0027712000
_diffrn_orient_matrix_UB_32      -0.0695254000
_diffrn_orient_matrix_UB_33      0.0047320000
_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  0.1360
_diffrn_reflns_av_unetI/netI     0.1109
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.832
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            14826
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.832
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.153
_diffrn_reflns_theta_min         2.457
_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    0.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47398
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
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    1.329
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: EtOAc/pentane'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.420
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         4031
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.1325
_refine_ls_R_factor_gt           0.0729
_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^)+(0.1219P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1769
_refine_ls_wR_factor_ref         0.2126
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2285
_reflns_number_total             4031
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09309k2.cif
_cod_data_source_block           knm-039a-gpcfr1-acoet_pentane
_cod_database_code               1576662
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N'
_diffrn_oxdiff_digest_frames
;
01df15bb22b38074db78e7bca69f6d3907000258f82
;
_diffrn_oxdiff_digest_hkl
;
01f2c1fffa98b4e29ef75316ac33b81491e8df
;
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.01
_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.a Ternary CH refined with riding coordinates:
 C8(H8), C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 N24(H27), C9(H9), C12(H15), C3(H3), C15(H12), C13(H14), C22(H18), C6(H6),
 C18(H22), C10(H10), C4(H4), C14(H13), C5(H5), C21(H19), C19(H21), C20(H20)
2.c Idealised Me refined as rotating group:
 C28(H30A,H30B,H30C)
;
_shelx_res_checksum              31672
_olex2_exptl_crystal_mounting_method loop
_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 3.274
_oxdiff_exptl_absorpt_empirical_full_min 0.447