Silver-Catalysed Intermolecular Benzylic-Selective C–H Amidation via Nitrene Transfer
Panja, Subir; Trinh, Tuan Anh; Warrington, Ethan M.; Hu, Derek B.; Garman, Leah C.; Guzei, Ilia; Schomaker, Jennifer; Chemical Science  (2026) –; doi:10.1039/D5SC10184K

data_1576892
_publ_section_title
;
 Silver-catalysed intermolecular benzylic-selective C-H amidation
 <i>via</i> nitrene transfer.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              9264
_journal_page_last               9269
_journal_paper_doi               10.1039/d5sc10184k
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety
'C54 H71.338 Ag2 N6 O0.669, 2(C2 F6 N O4 S2), 0.5[CH2Cl2]'
_chemical_formula_sum            'C58.5 H72.34 Ag2 Cl F12 N8 O8.67 S4'
_chemical_formula_weight         1633.71
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-29 deposited with the CCDC.	2026-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                84.243(6)
_cell_angle_beta                 83.807(7)
_cell_angle_gamma                77.184(7)
_cell_formula_units_Z            2
_cell_length_a                   10.7205(19)
_cell_length_b                   15.731(3)
_cell_length_c                   21.503(4)
_cell_measurement_reflns_used    9638
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      27.0620
_cell_measurement_theta_min      2.2418
_cell_volume                     3504.4(11)
_computing_cell_refinement       'SAINT+ V8.41 (Bruker AXS LLC, 1997-2024)'
_computing_data_collection       'APEX6 Ver. 2024.9-0. (Bruker AXS LLC, 2024)'
_computing_data_reduction        'SAINT+ V8.41 (Bruker AXS LLC, 1997-2024)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2019/1)'
_computing_structure_solution    'XT (Sheldrick, 2018/2)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00
_diffrn_crystal_treatment        'flash cooled with cold N~2~ gas'
_diffrn_detector                 '100 x 140 mm^2^ CMOS sensor'
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      'Oxford Cryostream 800'
_diffrn_measurement_device       '\k-geometry four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       ' \w and \f scans'
_diffrn_measurement_specimen_support 'MiTeGen mount'
_diffrn_radiation_collimation    'focusing mirror'
_diffrn_radiation_detector       'Bruker PHOTON III'
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            135287
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.107
_diffrn_reflns_theta_min         1.911
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.6
_diffrn_source_power             0.08
_diffrn_source_type              'Incoatec I\mS Diamond II'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.805
_exptl_absorpt_correction_T_max  0.3330
_exptl_absorpt_correction_T_min  0.3056
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1663
_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.059
_refine_diff_density_max         0.979
_refine_diff_density_min         -1.526
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1167
_refine_ls_number_reflns         15442
_refine_ls_number_restraints     1094
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0342P)^2^+4.0565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0772
_refine_ls_wR_factor_ref         0.0809
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13787
_reflns_number_total             15442
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc10184k2.cif
_cod_data_source_block           schomaker125a
_cod_depositor_comments
'Adding full bibliography for 1576891--1576892.cif.'
_cod_original_cell_volume        3504.5(11)
_cod_original_formula_sum        'C58.50 H72.34 Ag2 Cl F12 N8 O8.67 S4'
_cod_database_code               1576892
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.920
_diffrn_measurement_specimen_attachment_type 'paratone oil'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 F13-C59 \\sim F14-C59 \\sim F15-C59 \\sim F16-C60 \\sim F17-C60 \\sim F18-C60
\\sim F1-C55 \\sim F2-C55 \\sim
 F3-C55
 with sigma of 0.01
 S1A-C55A \\sim S1-C55 \\sim S6-C60
 with sigma of 0.01
 S1A-O2A \\sim S2-O5
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1 \\sim S2 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim O2
\\sim O3 \\sim O4 \\sim O5 \\sim N7 \\sim C55 \\sim C56 \\sim S1A \\sim S2A
\\sim F1A \\sim F2A \\sim F3A \\sim F4A \\sim F5A \\sim F6A \\sim O2A \\sim O3A
\\sim O4A \\sim O5A \\sim N7A \\sim C55A \\sim C56A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
S5 \\sim S6 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17 \\sim F18 \\sim
O10 \\sim O11 \\sim O12 \\sim O13 \\sim N9 \\sim C59 \\sim C60: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C51 \\sim C52 \\sim C52A \\sim C53 \\sim C53A \\sim C54 \\sim C54A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(O1A) = Uanis(O1)
4. Rigid body (RIGU) restrains
 S1, S2, F1, F2, F3, F4, F5, F6, O2, O3, O4, O5, N7, C55, C56, S1A, S2A, F1A,
 F2A, F3A, F4A, F5A, F6A, O2A, O3A, O4A, O5A, N7A, C55A, C56A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S5, S6, F13, F14, F15, F16, F17, F18, O10, O11, O12, O13, N9, C59, C60
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C51, C52, C52A, C53, C53A, C54, C54A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C48, C51, C52A, C54A, C53A} sigma for 1-2: 0.005, 1-3: 0.01
{C48, C51, C54, C52, C53} sigma for 1-2: 0.005, 1-3: 0.01
{C48, C51, C52, C53, C54} sigma for 1-2: 0.005, 1-3: 0.01
{C48, C51, C54A, C53A, C52A} sigma for 1-2: 0.005, 1-3: 0.01
{C48, C51, C53A, C52A, C54A} sigma for 1-2: 0.005, 1-3: 0.01
{C48, C51, C53, C54, C52} sigma for 1-2: 0.005, 1-3: 0.01
as in
{C12, C15, C16, C17, C18}
6. Others
 Sof(S1A)=Sof(S2A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=
 Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(N7A)=Sof(C55A)=Sof(C56A)=1-FVAR(1)
 Sof(S1)=Sof(S2)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O2)=
 Sof(O3)=Sof(O4)=Sof(O5)=Sof(N7)=Sof(C55)=Sof(C56)=FVAR(1)
 Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=Sof(H53D)=Sof(H53E)=
 Sof(H53F)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=1-FVAR(2)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(2)
 Sof(O1)=Sof(H1A)=Sof(H1B)=FVAR(3)
 Sof(O1A)=Sof(H1AA)=Sof(H1AB)=FVAR(4)
 Fixed Sof: S3(0.5) S4(0.5) F7(0.5) F8(0.5) F9(0.5) F10(0.5) F11(0.5) F12(0.5)
 O6(0.5) O7(0.5) O8(0.5) O9(0.5) N8(0.5) C57(0.5) C58(0.5) S5(0.5) S6(0.5)
 F13(0.5) F14(0.5) F15(0.5) F16(0.5) F17(0.5) F18(0.5) O10(0.5) O11(0.5)
 O12(0.5) O13(0.5) N9(0.5) C59(0.5) C60(0.5)
7.a Free rotating group:
 O1(H1A,H1B)
7.b Rotating group:
 O1A(H1AA,H1AB)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C11(H11), C13(H13), C20(H20), C22(H22), C23(H23),
 C28(H28), C29(H29), C31(H31), C38(H38), C40(H40), C47(H47), C49(H49), C50(H50)
7.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C25(H25A,H25B,H25C),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C), C52(H52A,H52B,H52C), C52A(H52D,H52E,H52F), C53(H53A,H53B,H53C),
 C53A(H53D,H53E,H53F), C54(H54A,H54B,H54C), C54A(H54D,H54E,H54F), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 44 electrons were 
found in a volume of 246\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.5[CH2Cl2] per Asymmetric Unit 
which account for 42 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              38766
_shelx_fab_checksum              30275
_olex2_submission_special_instructions 'No special instructions were received'