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_7161031
_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         'C49 H42 N2 O4'
_chemical_formula_sum            'C49 H41 N2 O4'
_chemical_formula_weight         721.84
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.6572(16)
_cell_length_b                   20.628(2)
_cell_length_c                   29.589(4)
_cell_measurement_reflns_used    9779
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      68.25
_cell_measurement_theta_min      2.99
_cell_volume                     7725.5(16)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0781
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            99883
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.629
_diffrn_reflns_theta_min         2.987
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.621
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4095
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1519 before and 0.0829 after correction.
The Ratio of minimum to maximum transmission is 0.5438.
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    1.241
_exptl_crystal_description       block
_exptl_crystal_F_000             3048
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.670
_refine_diff_density_min         -0.661
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         7118
_refine_ls_number_restraints     827
_refine_ls_restrained_S_all      1.554
_refine_ls_R_factor_all          0.1064
_refine_ls_R_factor_gt           0.0956
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1352P)^2^+5.3631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2651
_refine_ls_wR_factor_ref         0.2765
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5878
_reflns_number_total             7118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01818h2.cif
_cod_data_source_block           cu_20250623q_0m_a
_cod_database_code               7161031
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.845
_shelx_estimated_absorpt_t_min   0.836
_olex2_refinement_description
;
1. Restrained distances
 O6A-C45A
 2.1 with sigma of 0.001
 O6A-O5A
 2.1 with sigma of 0.001
 N2-C37 \\sim N2-C37A
 with sigma of 0.02
 C39-C38 \\sim C39-C38A
 with sigma of 0.02
 C39-C37 \\sim C39-C37A
 with sigma of 0.02
 C39-C40 \\sim C39-C40A
 with sigma of 0.02
 C38-C43 \\sim C38A-C43A
 with sigma of 0.02
 C37-C36 \\sim C37A-C36A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 C43-C42 \\sim C43A-C42A
 with sigma of 0.02
 C42-C41 \\sim C42A-C41A
 with sigma of 0.02
 N2-C36 \\sim N2-C36A
 with sigma of 0.04
 C39-C43 \\sim C39-C43A
 with sigma of 0.04
 C39-C41 \\sim C39-C41A
 with sigma of 0.04
 C39-C36 \\sim C39-C36A
 with sigma of 0.04
 C38-C42 \\sim C38A-C42A
 with sigma of 0.04
 C40-C42 \\sim C40A-C42A
 with sigma of 0.04
 C43-C41 \\sim C43A-C41A
 with sigma of 0.04
 N2-C37 \\sim N2-C37A \\sim C37A-C36A \\sim C37-C36 \\sim C40-C39 \\sim C39-C37
\\sim C39-C37A \\sim C40A-
 C39 \\sim C39-C38 \\sim C39-C38A \\sim C43-C38 \\sim C43A-C38A \\sim C43-C42
\\sim C43A-C42A \\sim C42A-
 C41A \\sim C42-C41 \\sim C41A-C40A \\sim C41-C40
 with sigma of 0.02
 O2-C45 \\sim O5A-C45A
 with sigma of 0.02
 O2-C44 \\sim O5A-C44A
 with sigma of 0.02
 C12-C44 \\sim C12-C44A
 with sigma of 0.02
 O1-C44 \\sim O6A-C44A
 with sigma of 0.02
 C46-C45 \\sim C46A-C45A
 with sigma of 0.02
 O2-C12 \\sim O5A-C12
 with sigma of 0.04
 O2-O1 \\sim O5A-O6A
 with sigma of 0.04
 O2-C46 \\sim O5A-C46A
 with sigma of 0.04
 C12-O1 \\sim C12-O6A
 with sigma of 0.04
 C45-C44 \\sim C45A-C44A
 with sigma of 0.04
 C44-C12 \\sim C44A-C12 \\sim O1-C44 \\sim O6A-C44A \\sim O5A-C44A \\sim O2-C44
\\sim O5A-C45A \\sim O2-
 C45 \\sim C46-C45 \\sim C46A-C45A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C39 \\sim C38 \\sim C37 \\sim C40 \\sim C43 \\sim C42 \\sim C41 \\sim C36 \\sim
C38A \\sim C37A \\sim C40A \\sim C43A \\sim C42A \\sim C41A \\sim C36A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O2 \\sim O1 \\sim C46 \\sim C45 \\sim C44 \\sim O5A \\sim O6A \\sim C46A \\sim
C45A \\sim C44A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C12 \\sim C44A \\sim C44 \\sim O2 \\sim O5A \\sim O1 \\sim O6A \\sim C45A \\sim
C46A \\sim C46 \\sim C45: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C12 \\sim C44A \\sim C11 \\sim C13 \\sim C47: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C47 \\sim O3 \\sim O4: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C14 \\sim C10 \\sim C11 \\sim C12 \\sim C13: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C11)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
Uanis(O4) \\sim Ueq, Uanis(C47) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
3. Rigid body (RIGU) restrains
 C36, C37, C39, C38, C43, C42, C41, C40, N2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N2, C37A, C36A, C39, C40A, C41A, C43A, C38A, C42A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C44, O2, C45, C46, O1, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C12, C44A, O6A, O5A, C45A, C46A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Others
 Sof(C38A)=Sof(H38A)=Sof(C37A)=Sof(H37A)=Sof(C40A)=Sof(H40A)=Sof(C43A)=
 Sof(H43A)=Sof(C42A)=Sof(H42A)=Sof(C41A)=Sof(H41A)=Sof(C36A)=Sof(H36D)=
 Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(C38)=Sof(H38)=Sof(C37)=Sof(H37)=Sof(C40)=Sof(H40)=Sof(C43)=Sof(H43)=
 Sof(C42)=Sof(H42)=Sof(C41)=Sof(H41)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 FVAR(1)
 Sof(O5A)=Sof(O6A)=Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C45A)=Sof(H45C)=
 Sof(H45D)=Sof(C44A)=1-FVAR(2)
 Sof(O2)=Sof(O1)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=Sof(C44)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C37(H37), C37A(H37A)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C48(H48A,H48B), C45(H45A,H45B), C45A(H45C,H45D)
5.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C23(H23), C25(H25), C28(H28), C19(H19), C31(H31), C26(H26),
 C34(H34), C27(H27), C1(H1), C32(H32), C22(H22), C33(H33), C20(H20), C38(H38),
 C21(H21), C5(H5), C2(H2), C3(H3), C40(H40), C4(H4), C43(H43), C42(H42),
 C41(H41), C38A(H38A), C40A(H40A), C43A(H43A), C42A(H42A), C41A(H41A)
5.d Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C46(H46A,H46B,H46C), C36(H36A,H36B,H36C), C36A(H36D,H36E,
 H36F), C46A(H46D,H46E,H46F)
;
_shelx_res_checksum              87192
_olex2_submission_special_instructions 'No special instructions were received'