Tribromide enabled step-up generation of spirolactams from esters employing oxidative dearomatization of arenols.
Roy, Barnali; Avasare, Vidya; Sarkar, Debayan; Chemical communications (Cambridge, England) 60 (2024) 9206–9209; doi:10.1039/d4cc02527j

data_7133435
_publ_section_title
;
 Tribromide enabled step-up generation of spirolactams from esters
 employing oxidative dearomatization of arenols.
;
_journal_issue                   69
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9206
_journal_page_last               9209
_journal_paper_doi               10.1039/d4cc02527j
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         '2(C19 H22 F N O2)'
_chemical_formula_sum            'C38 H44 F2 N2 O4'
_chemical_formula_weight         630.75
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-09-23 deposited with the CCDC.	2024-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.169(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6691(5)
_cell_length_b                   21.3606(11)
_cell_length_c                   18.6802(11)
_cell_measurement_reflns_used    6638
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.2540
_cell_measurement_theta_min      1.9100
_cell_volume                     3414.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.928
_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    -15.00  96.00   0.50   35.29    --   10.00  82.00 -30.00  222
  2  \w    -78.00  29.00   0.50   35.29    --   10.00 -77.00-120.00  214
  3  \w    -12.00  93.00   0.50   35.29    --   10.00  82.00  60.00  210
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0093156000
_diffrn_orient_matrix_UB_12      -0.0320926000
_diffrn_orient_matrix_UB_13      -0.0092662000
_diffrn_orient_matrix_UB_21      -0.0373441000
_diffrn_orient_matrix_UB_22      0.0083825000
_diffrn_orient_matrix_UB_23      -0.0352969000
_diffrn_orient_matrix_UB_31      0.0735233000
_diffrn_orient_matrix_UB_32      0.0002072000
_diffrn_orient_matrix_UB_33      -0.0121403000
_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  0.0346
_diffrn_reflns_av_unetI/netI     0.0511
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            19547
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.094
_diffrn_reflns_theta_min         1.907
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_F_000             1344
_refine_diff_density_max         0.262
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0024(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.961
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         6971
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.961
_refine_ls_R_factor_all          0.1094
_refine_ls_R_factor_gt           0.0536
_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^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1332
_refine_ls_wR_factor_ref         0.1552
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3633
_reflns_number_total             6971
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02527j2.cif
_cod_data_source_block           dspkspamd2nd_261121
_cod_depositor_comments          'Adding full bibliography for 7133435.cif.'
_cod_database_code               7133435
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H22 F N O2'
_reflns_odcompleteness_completeness 98.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H008 of O008, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H005 of O005
2.a Ternary CH refined with riding coordinates:
 C00M(H00M), C00R(H00R), C00U(H00U), C00V(H00V)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00F(H00E,H00F), C00X(H00G,H00I), C00Y(H00C,H00D)
2.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00J(H00J), C00K(H00K), C00N(H00N), C00P(H00P), C00T(H00T),
 C00W(H00W), C00Z(H00Z), C010(H010), C011(H011), C013(H013), C014(H014)
2.d Idealised Me refined as rotating group:
 C015(H01A,H01B,H01C), C016(H01J,H01K,H01L), C017(H01M,H01N,H01O), C018(H01D,
 H01E,H01F), C019(H01P,H01Q,H01R), C01A(H01G,H01H,H01I)
2.e Idealised tetrahedral OH refined as rotating group:
 O005(H005)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              10554
_shelx_hkl_checksum              22806
_shelx_fab_checksum              55477
_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 3.196
_oxdiff_exptl_absorpt_empirical_full_min 0.315