Silver- and gold-catalyzed divergent cascade cycloisomerization/[3 + 2] <i>versus</i> [2 + 2 + 1] cycloaddition towards a stereoselective access to heterohexacyclic derivatives.
Gentilini, Emilie; Bouschon, Anaïs; Davenel, Vincent; Fontaine-Vive, Fabien; Fourquez, Jean-Marie; Michelet, Véronique; Chemical science 16 (2025) 17611–17620; doi:10.1039/d5sc05338b

data_1575659
_publ_section_title
;
 Silver- and gold-catalyzed divergent cascade cycloisomerization/[3 + 2]
 <i>versus</i> [2 + 2 + 1] cycloaddition towards a stereoselective access
 to heterohexacyclic derivatives.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              17611
_journal_page_last               17620
_journal_paper_doi               10.1039/d5sc05338b
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C25 H25 N O5'
_chemical_formula_sum            'C25 H25 N O5'
_chemical_formula_weight         419.46
_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             2023-12-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-12 deposited with the CCDC.	2025-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.849(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5471(4)
_cell_length_b                   16.4155(7)
_cell_length_c                   11.7506(5)
_cell_measurement_reflns_used    7023
_cell_measurement_temperature    295
_cell_measurement_theta_max      30.4250
_cell_measurement_theta_min      4.3430
_cell_volume                     2142.67(15)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      295
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3045
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.880
_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    -21.00   4.00   1.00   30.00    --   14.59 -79.00  60.00   25
  2  \w    -38.00 -13.00   1.00   30.00    --  -15.53  79.00-175.00   25
  3  \w    -37.00 -12.00   1.00   30.00    --  -15.53 -79.00  60.00   25
  4  \w     -7.00  84.00   1.00   30.00    --   14.59  38.00 120.00   91
  5  \w     -9.00  88.00   1.00   30.00    --   14.59  38.00  30.00   97
  6  \w    -42.00  12.00   1.00   30.00    --  -15.53 -77.00 150.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0037503000
_diffrn_orient_matrix_UB_12      -0.0198059000
_diffrn_orient_matrix_UB_13      0.0525228000
_diffrn_orient_matrix_UB_21      -0.0392090000
_diffrn_orient_matrix_UB_22      0.0309779000
_diffrn_orient_matrix_UB_23      0.0094135000
_diffrn_orient_matrix_UB_31      -0.0502457000
_diffrn_orient_matrix_UB_32      -0.0226800000
_diffrn_orient_matrix_UB_33      -0.0330672000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.880
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            18807
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.880
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.157
_diffrn_reflns_theta_min         3.155
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.091
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70734
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
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    1.300
_exptl_crystal_description       prism
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.520
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         6093
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0618
_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^)+(0.0788P)^2^+1.1084P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1676
_refine_ls_wR_factor_ref         0.1849
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4607
_reflns_number_total             6093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05338b2.cif
_cod_data_source_block           emg_d
_cod_depositor_comments
'Adding full bibliography for 1575658--1575659.cif.'
_cod_database_code               1575659
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.972
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C8(H8A,H8B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C20(H20), C21(H21)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              48638
_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 1.317
_oxdiff_exptl_absorpt_empirical_full_min 0.692