Three-component tandem benzyl-C(sp<sup>3</sup>)-H functionalization <i>via</i> thermally generated arynes with phenazine.
Zhang, Yajuan; Chai, Fuxiang; Hu, Qiong; Chang, Meng; Qiang, Ruihua; Hu, Yimin; Organic & biomolecular chemistry 24 (2026) 1231–1236; doi:10.1039/d5ob01818h

data_7161025
_publ_section_title
;
 Three-component tandem benzyl-C(sp<sup>3</sup>)-H functionalization
 <i>via</i> thermally generated arynes with phenazine.
;
_journal_issue                   6
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1231
_journal_page_last               1236
_journal_paper_doi               10.1039/d5ob01818h
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C75 H66 N2 O9'
_chemical_formula_sum            'C75 H66 N2 O9'
_chemical_formula_weight         1139.29
_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
_audit_creation_date             2025-06-30
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-10-07 deposited with the CCDC.	2025-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                61.643(2)
_cell_angle_beta                 82.789(3)
_cell_angle_gamma                74.741(4)
_cell_formula_units_Z            2
_cell_length_a                   15.3348(9)
_cell_length_b                   15.7859(9)
_cell_length_c                   16.1062(9)
_cell_measurement_reflns_used    9758
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      62.265
_cell_measurement_theta_min      2.987
_cell_volume                     3310.1(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0833
_diffrn_reflns_av_unetI/netI     0.0678
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            53948
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.381
_diffrn_reflns_theta_min         2.987
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.596
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4397
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1096 before and 0.0755 after correction. The Ratio of minimum to maximum transmission is 0.5839. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.143
_exptl_crystal_description       block
_exptl_crystal_F_000             1204
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.634
_refine_diff_density_min         -0.599
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     903
_refine_ls_number_reflns         12134
_refine_ls_number_restraints     933
_refine_ls_restrained_S_all      1.150
_refine_ls_R_factor_all          0.1429
_refine_ls_R_factor_gt           0.1002
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1912P)^2^+0.7554P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2940
_refine_ls_wR_factor_ref         0.3417
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6914
_reflns_number_total             12134
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01818h2.cif
_cod_data_source_block           cu_20250413b_0m_a
_cod_database_code               7161025
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.900
_olex2_refinement_description
;
1. Restrained distances
 C4A-C19 \\sim C21-C19 \\sim C8A-C19 \\sim C20-C19
 with sigma of 0.02
 C6-C0 \\sim C5-C6 \\sim C02B-C0 \\sim C4-C5 \\sim C2-C3 \\sim C3A-C01{ \\sim
C2-C1 \\sim C3A-C2A \\sim C02B-
 C01{ \\sim C1-C6 \\sim C2A-C6 \\sim C4-C3
 with sigma of 0.02
 C64-C63 \\sim C63-C3AA \\sim C3AA-C6AA \\sim C65-C64 \\sim C68-C63 \\sim
C67-C68 \\sim C67-C66 \\sim C65-
 C66 \\sim C1AA-C6AA \\sim C0AA-C5AA \\sim C1AA-C5AA \\sim C0AA-C63
 with sigma of 0.02
 C59-C58 \\sim C2AA-C9AA \\sim C60-C58 \\sim C2AA-C7AA \\sim O7-C2AA \\sim
O7-C58
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C6 \\sim C3 \\sim C5 \\sim C4 \\sim C1 \\sim C2 \\sim C01{ \\sim C0 \\sim C02B
\\sim C2A \\sim C3A: within 2A with sigma of 0.001 and sigma for terminal atoms
of 0.002 within 2A
C19 \\sim C21 \\sim C20 \\sim C8A \\sim C4A: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C63 \\sim C68 \\sim C66 \\sim C64 \\sim C67 \\sim C65 \\sim C0AA \\sim C1AA
\\sim C3AA \\sim C5AA \\sim C6AA: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C68 \\sim C66 \\sim C64 \\sim C67 \\sim C65 \\sim C0AA \\sim C1AA \\sim C3AA
\\sim C5AA \\sim C6AA \\sim C63: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C58 \\sim C60 \\sim C59: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C54 \\sim C55 \\sim C56: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C58 \\sim C60 \\sim C59 \\sim C2AA \\sim C7AA \\sim C9AA: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
O7 \\sim C58 \\sim C60 \\sim C59 \\sim C2AA \\sim C7AA \\sim C9AA: within 2A
with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
O4 \\sim O3 \\sim C18 \\sim C19 \\sim C21 \\sim C20 \\sim C8A \\sim C4A: within
2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C15 \\sim C18: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C14 \\sim C16 \\sim C15 \\sim C17 \\sim C13 \\sim C12: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
Uanis(C3) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(C2) \\sim Ueq, Uanis(C01{) \\sim Ueq, Uanis(C0) \\sim Ueq,
Uanis(C02B) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C6)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C19) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C4A)
\\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
3. Rigid body (RIGU) restrains
 C19, C20, C21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C8A, C19, C4A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C6, C1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C6, C0, C02B, C01{, C3A, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C63, C68, C67, C66, C65, C64
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C63, C3AA, C6AA, C1AA, C5AA, C0AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C58, C59, C60
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C2AA, C7AA, C9AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Others
 Sof(H19A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=1-FVAR(1)
 Sof(H19)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=FVAR(1)
 Sof(C01{)=Sof(H01{)=Sof(C02B)=Sof(H02B)=Sof(C0)=Sof(H0)=Sof(C2A)=Sof(H2A)=
 Sof(C3A)=Sof(H3A)=1-FVAR(2)
 Sof(C3)=Sof(H3)=Sof(C5)=Sof(H5)=Sof(C4)=Sof(H4)=Sof(C1)=Sof(H1)=Sof(C2)=
 Sof(H2)=FVAR(2)
 Sof(C1AA)=Sof(H1AA)=Sof(C5AA)=Sof(H5AA)=Sof(C0AA)=Sof(H0AA)=Sof(C3AA)=
 Sof(H3AA)=Sof(C6AA)=Sof(H6AA)=1-FVAR(3)
 Sof(C68)=Sof(H68)=Sof(C66)=Sof(H66)=Sof(C64)=Sof(H64)=Sof(C67)=Sof(H67)=
 Sof(C65)=Sof(H65)=FVAR(3)
 Sof(C2AA)=Sof(H2AA)=Sof(C7AA)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C9AA)=
 Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(4)
 Sof(C58)=Sof(H58)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C59)=Sof(H59A)=
 Sof(H59B)=Sof(H59C)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C23(H23), C54(H54), C58(H58), C19(H19), C19(H19A), C2AA(H2AA)
5.b Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C16(H16A,H16B), C14(H14A,H14B), C48(H48A,H48B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C41(H41), C42(H42), C40(H40), C33(H33), C35(H35), C34(H34),
 C73(H73), C71(H71), C26(H26), C30(H30), C69(H69), C68(H68), C72(H72), C27(H27),
  C28(H28), C70(H70), C66(H66), C3(H3), C29(H29), C64(H64), C67(H67), C5(H5),
 C65(H65), C4(H4), C1(H1), C2(H2), C01{(H01{), C02B(H02B), C0(H0), C2A(H2A),
 C3A(H3A), C1AA(H1AA), C5AA(H5AA), C0AA(H0AA), C3AA(H3AA), C6AA(H6AA)
5.d Fitted hexagon refined as free rotating group:
 C01{(C02B,C0,C6,C2A,C3A), C1AA(C5AA,C0AA,C63,C3AA,C6AA)
5.e Idealised Me refined as rotating group:
 C75(H75A,H75B,H75C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C60(H60A,H60B,
 H60C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C59(H59A,H59B,H59C), C21(H21A,
 H21B,H21C), C20(H20A,H20B,H20C), C8A(H8AA,H8AB,H8AC), C4A(H4AA,H4AB,H4AC),
 C7AA(H7AA,H7AB,H7AC), C9AA(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              62875
_shelx_fab_checksum              10106
_olex2_submission_special_instructions 'No special instructions were received'