BF3·OEt2-Mediated Nucleophilic Fluorocyclization of Sulfonyl 3-Methylene-oxabenzocyclooctan-6-ones. Diastereocontrolled Synthesis of Benzofused Fluorooxabicyclo[4.2.1]nonanes
Hsueh, Nai-Chen; Chang, Meng-Yang; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01459A

data_7158872
_publ_section_title
;
 BF3&#x00B7;OEt2-Mediated Nucleophilic Fluorocyclization of Sulfonyl
 3-Methylene-oxabenzocyclooctan-6-ones. Diastereocontrolled Synthesis of
 Benzofused Fluorooxabicyclo[4.2.1]nonanes
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01459A
_journal_year                    2022
_chemical_formula_moiety         'C19 H19 F O3 S'
_chemical_formula_sum            'C19 H19 F O3 S'
_chemical_formula_weight         346.40
_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             2019-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-11 deposited with the CCDC.	2022-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                88.093(4)
_cell_angle_beta                 81.665(4)
_cell_angle_gamma                73.510(4)
_cell_formula_units_Z            2
_cell_length_a                   8.1798(3)
_cell_length_b                   8.2382(4)
_cell_length_c                   12.9438(7)
_cell_measurement_reflns_used    6654
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.8700
_cell_measurement_theta_min      2.5740
_cell_volume                     827.50(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.36a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.36a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.36a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      113(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 0.938
_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      4.00  29.00   0.50    1.23    --   10.60 -80.00 -83.00   50
  2  \w     14.00  40.00   0.50    1.23    --   10.60  80.00  39.00   52
  3  \w    -67.00 -42.00   0.50    1.23    --  -10.90 -80.00 -83.00   50
  4  \w     16.00  42.00   0.50    1.23    --  -10.90  80.00  39.00   52
  5  \w     -3.00  72.00   0.50    1.23    --   10.60  82.00 -90.00  150
  6  \w    -16.00  21.00   0.50    1.23    --   10.60  82.00-120.00   74
  7  \w     33.00  70.00   0.50    1.23    --   10.60  82.00-120.00   74
  8  \w      0.00  26.00   0.50    1.23    --   10.60  82.00  90.00   52
  9  \w    -26.00  23.00   0.50    1.23    --   10.60  38.00 120.00   98
 10  \w     71.00 100.00   0.50    1.23    --   10.60  38.00 120.00   58
 11  \w     -7.00  22.00   0.50    1.23    --   10.60  82.00  60.00   58
 12  \w     51.00  97.00   0.50    1.23    --   10.60  82.00  60.00   92
 13  \w    -69.00  35.00   0.50    1.23    --   10.60 -82.00-150.00  208
 14  \w     14.00  75.00   0.50    1.23    --   10.60  77.00 150.00  122
 15  \w    -79.00 -34.00   0.50    1.23    --   10.60 -77.00-180.00   90
 16  \w     -9.00  17.00   0.50    1.23    --   10.60 -77.00-180.00   52
 17  \w    -10.00  38.00   0.50    1.23    --   10.60  82.00   0.00   96
 18  \w     20.00  60.00   0.50    1.23    --  -10.90  77.00 120.00   80
 19  \w    -36.00   2.00   0.50    1.23    --  -10.90  77.00 120.00   76
 20  \w    -96.00   6.00   0.50    1.23    --  -10.90 -82.00  60.00  204
;
_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      0.0059692000
_diffrn_orient_matrix_UB_12      0.0462940000
_diffrn_orient_matrix_UB_13      0.0438569000
_diffrn_orient_matrix_UB_21      0.0885243000
_diffrn_orient_matrix_UB_22      -0.0105440000
_diffrn_orient_matrix_UB_23      -0.0180642000
_diffrn_orient_matrix_UB_31      -0.0217466000
_diffrn_orient_matrix_UB_32      0.0762156000
_diffrn_orient_matrix_UB_33      -0.0285970000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0379
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12519
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.055
_diffrn_reflns_theta_min         2.578
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.220
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56378
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.36a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       block
_exptl_crystal_F_000             364
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.426
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.009(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3425
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0397P)^2^+0.3883P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0928
_refine_ls_wR_factor_ref         0.0971
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2907
_reflns_number_total             3425
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01459a2.cif
_cod_data_source_block           nc8rnb
_cod_database_code               7158872
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C18 H19 O4 S1'
_diffrn_oxdiff_digest_frames
;
0187d8a2b1becebaa6ef6818b76f64d4bd00027ada2
;
_diffrn_oxdiff_digest_hkl
;
0199f794fe159d59089b6d239a6b7ab34893af
;
_reflns_odcompleteness_completeness 98.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C4(H4), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_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 1.526
_oxdiff_exptl_absorpt_empirical_full_min 0.726