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_7161028
_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         '2(C51 H46 N2 O4)'
_chemical_formula_sum            'C102 H92 N4 O8'
_chemical_formula_weight         1501.79
_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                83.9390(10)
_cell_angle_beta                 88.4140(10)
_cell_angle_gamma                74.4480(10)
_cell_formula_units_Z            2
_cell_length_a                   12.2666(3)
_cell_length_b                   12.8960(3)
_cell_length_c                   27.5494(6)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      68.290
_cell_measurement_theta_min      3.227
_cell_volume                     4175.01(17)
_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 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.0662
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            56976
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.367
_diffrn_reflns_theta_min         3.226
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.592
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5295
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1138 before and 0.0731 after correction.
The Ratio of minimum to maximum transmission is 0.7031.
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    1.195
_exptl_crystal_description       block
_exptl_crystal_F_000             1592
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1106
_refine_ls_number_reflns         15269
_refine_ls_number_restraints     321
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0521
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0821P)^2^+0.3692P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1439
_refine_ls_wR_factor_ref         0.1592
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10977
_reflns_number_total             15269
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01818h2.cif
_cod_data_source_block           cu_20250427f_0m_a
_cod_database_code               7161028
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.861
_shelx_estimated_absorpt_t_min   0.852
_olex2_refinement_description
;
1. Restrained distances
 C21-C19 \\sim C21A-C19 \\sim C20A-C19 \\sim C20-C19
 with sigma of 0.02
 C22-C15 \\sim C22A-C15 \\sim O2A-C22A \\sim O2-C22 \\sim O2-C23 \\sim O2A-C23A
\\sim C24A-C23A \\sim C24-
 C23 \\sim C25-C23 \\sim C25A-C23A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C70 \\sim C72 \\sim C71: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C19 \\sim C20 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C19 \\sim C20 \\sim C21 \\sim C20A \\sim C21A: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002 within 2A
C23 \\sim C24 \\sim C25 \\sim O2: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C22 \\sim C22A \\sim O2 \\sim C23 \\sim C24 \\sim C25 \\sim O2A \\sim C23A
\\sim C24A \\sim C25A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O4 \\sim C19: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C23) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(O2)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C20, C19, C21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C19, C20A, C21A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C22, O2, C23, C24, C25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C22A, O2A, C23A, C24A, C25A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Others
 Sof(H19A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=
 Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=FVAR(1)
 Sof(O2A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=
 Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C22A)=1-FVAR(2)
 Sof(O2)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C70(H70), C19(H19), C19(H19A), C74(H74), C23(H23), C23A(H23A)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C65(H65A,H65B), C67(H67A,H67B), C14(H14A,H14B), C95(H95A,
 H95B), C44(H44A,H44B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C62(H62), C39(H39), C26(H26), C77(H77), C30(H30), C42(H42), C5(H5),
 C81(H81), C40(H40), C90(H90), C101(H101), C1(H1), C56(H56), C80(H80), C93(H93),
  C41(H41), C79(H79), C84(H84), C52(H52), C4(H4), C29(H29), C50(H50), C2(H2),
 C91(H91), C46(H46), C33(H33), C27(H27), C3(H3), C92(H92), C78(H78), C53(H53),
 C87(H87), C28(H28), C36(H36), C85(H85), C55(H55), C48(H48), C47(H47), C34(H34),
  C86(H86), C54(H54), C35(H35), C97(H97), C99(H99), C98(H98)
5.d Idealised Me refined as rotating group:
 C102(H10A,H10B,H10C), C20(H20A,H20B,H20C), C51(H51A,H51B,H51C), C72(H72A,H72B,
 H72C), C24(H24A,H24B,H24C), C76(H76A,H76B,H76C), C25(H25A,H25B,H25C), C71(H71A,
 H71B,H71C), C75(H75A,H75B,H75C), C21(H21A,H21B,H21C), C20A(H20D,H20E,H20F),
 C21A(H21D,H21E,H21F), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F)
;
_shelx_res_checksum              17049
_olex2_submission_special_instructions 'No special instructions were received'