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_7158873
_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         'C18 H17 F O3 S'
_chemical_formula_sum            'C18 H17 F O3 S'
_chemical_formula_weight         332.38
_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
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-09
_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                99.558(2)
_cell_angle_beta                 105.692(2)
_cell_angle_gamma                96.770(2)
_cell_formula_units_Z            2
_cell_length_a                   6.87130(10)
_cell_length_b                   10.4176(3)
_cell_length_c                   11.8932(3)
_cell_measurement_reflns_used    7422
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.9860
_cell_measurement_theta_min      2.0070
_cell_volume                     796.27(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.56a (Rigaku OD, 2020)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      113(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -45.00 -20.00   0.50    7.15    --   10.60 -80.00  42.00   50
  2  \w     42.00  67.00   0.50    7.15    --   10.60  80.00 165.00   50
  3  \w      1.00  27.00   0.50    7.15    --   10.60  80.00 165.00   52
  4  \w    -67.00 -42.00   0.50    7.15    --  -10.90 -80.00  42.00   50
  5  \w      7.00  35.00   0.50    7.15    --   10.60 -77.00 -60.00   56
  6  \w    -62.00 -36.00   0.50    7.15    --   10.60 -77.00 -30.00   52
  7  \w    -12.00  14.00   0.50    7.15    --   10.60 -82.00  30.00   52
  8  \w    -16.00  99.00   0.50    7.15    --   10.60  82.00 -90.00  230
  9  \w    -78.00  36.00   0.50    7.15    --   10.60 -77.00  90.00  228
 10  \w    -17.00  71.00   0.50    7.15    --   10.60  82.00  30.00  176
 11  \w    -21.00  17.00   0.50    7.15    --   10.60 -77.00 -30.00   76
 12  \w    -14.00  11.00   0.50    7.15    --   10.60  82.00  90.00   50
 13  \w    -79.00 -51.00   0.50    7.15    --   10.60 -82.00  30.00   56
 14  \w    -72.00 -46.00   0.50    7.15    --   10.60 -77.00 -60.00   52
 15  \w    -25.00  17.00   0.50    7.15    --  -10.90 -82.00   0.00   84
 16  \w    -97.00   7.00   0.50    7.15    --  -10.90 -77.00-180.00  208
 17  \w    -64.00 -38.00   0.50    7.15    --  -10.90 -82.00   0.00   52
 18  \w    -74.00   4.00   0.50    7.15    --  -10.90 -82.00 120.00  156
 19  \w    -99.00 -65.00   0.50    7.15    --  -10.90 -77.00 -90.00   68
 20  \w     22.00  54.00   0.50    7.15    --  -10.90  80.00 165.00   64
;
_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      -0.0350148000
_diffrn_orient_matrix_UB_12      -0.0611336000
_diffrn_orient_matrix_UB_13      0.0128733000
_diffrn_orient_matrix_UB_21      0.0163275000
_diffrn_orient_matrix_UB_22      -0.0341614000
_diffrn_orient_matrix_UB_23      -0.0525344000
_diffrn_orient_matrix_UB_31      0.1017463000
_diffrn_orient_matrix_UB_32      -0.0027018000
_diffrn_orient_matrix_UB_33      0.0329211000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0226
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            12550
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         1.82
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.226
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59039
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.56a (Rigaku Oxford Diffraction, 2020)
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    1.386
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.713
_refine_diff_density_min         -0.519
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3134
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0461P)^2^+0.5397P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1025
_refine_ls_wR_factor_ref         0.1059
_reflns_number_gt                2712
_reflns_number_total             3134
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d2ob01459a2.cif
_cod_data_source_block           nc1202nb
_cod_original_cell_volume        796.26(3)
_cod_database_code               7158873
_chemical_oxdiff_formula         'C18 H17 S1 O3 F1'
_diffrn_oxdiff_digest_frames
;
01542d3b515a656385ac5f93c1b47053d800025873e
;
_diffrn_oxdiff_digest_hkl
;
011ee2d9e15e2f0085946a79a690dcb258a77e
;
_reflns_odcompleteness_completeness 99.36
_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:
 C9(H9), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C14(H14), C15(H15), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_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 1.580
_oxdiff_exptl_absorpt_empirical_full_min 0.735