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_7158870
_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         'C16 H22 O3 S'
_chemical_formula_sum            'C16 H22 O3 S'
_chemical_formula_weight         294.39
_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             2020-02-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2020-05-11 deposited with the CCDC.	2022-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                105.346(3)
_cell_angle_beta                 92.676(2)
_cell_angle_gamma                102.631(3)
_cell_formula_units_Z            2
_cell_length_a                   5.5686(2)
_cell_length_b                   9.5682(3)
_cell_length_c                   15.1726(5)
_cell_measurement_reflns_used    9121
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.9310
_cell_measurement_theta_min      2.2610
_cell_volume                     756.02(5)
_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  'ShelXL (Sheldrick, 2015)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.953
_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    -17.00 100.00   0.50   20.02    --   10.60  82.00-180.00  234
  2  \w    -20.00 100.00   0.50   20.02    --   10.60  57.00 120.00  240
  3  \w    -15.00 100.00   0.50   20.02    --   10.60  77.00-120.00  230
  4  \w    -79.00  48.00   0.50   20.02    --   10.60 -38.00 -90.00  254
  5  \w    -20.00 100.00   0.50   20.02    --   10.60  57.00  30.00  240
  6  \w   -100.00  17.00   0.50   20.02    --  -10.90 -82.00-180.00  234
  7  \w   -100.00  15.00   0.50   20.02    --  -10.90 -77.00  30.00  230
  8  \w   -100.00  17.00   0.50   20.02    --  -10.90 -82.00 -30.00  234
  9  \w   -100.00  15.00   0.50   20.02    --  -10.90 -77.00-120.00  230
 10  \w    -38.00  70.00   0.50   20.02    --  -10.90  82.00-150.00  216
 11  \w    -41.00  79.00   0.50   20.02    --  -10.90  57.00 150.00  240
;
_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      -0.0369165000
_diffrn_orient_matrix_UB_12      -0.0669743000
_diffrn_orient_matrix_UB_13      -0.0364629000
_diffrn_orient_matrix_UB_21      -0.0035962000
_diffrn_orient_matrix_UB_22      0.0422189000
_diffrn_orient_matrix_UB_23      -0.0318519000
_diffrn_orient_matrix_UB_31      0.1260010000
_diffrn_orient_matrix_UB_32      0.0013782000
_diffrn_orient_matrix_UB_33      -0.0059427000
_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  0.0451
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16987
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.071
_diffrn_reflns_theta_min         2.274
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54500
_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    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             316
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         3170
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0572
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0639P)^2^+0.8050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1449
_refine_ls_wR_factor_ref         0.1489
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2685
_reflns_number_total             3170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01459a2.cif
_cod_data_source_block           nc1217nbf
_cod_database_code               7158870
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H22 O4 S1'
_diffrn_oxdiff_digest_frames
;
01e73e7a99737e7d7d71da12b6d046517600025949e
;
_diffrn_oxdiff_digest_hkl
;
0112c011c53c9855edf9b8ecf9c248db84e7cf
;
_reflns_odcompleteness_completeness 99.84
_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), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              90496
_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 1.617
_oxdiff_exptl_absorpt_empirical_full_min 0.593