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_7158876
_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 H23 Cl O4 S'
_chemical_formula_sum            'C19 H23 Cl O4 S'
_chemical_formula_weight         382.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-06-08 deposited with the CCDC.	2022-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 93.464(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.5435(3)
_cell_length_b                   6.0581(2)
_cell_length_c                   20.5872(4)
_cell_measurement_reflns_used    23575
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.9690
_cell_measurement_theta_min      2.7930
_cell_volume                     1810.54(8)
_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    -17.00 100.00   0.50    8.15    --   10.60  82.00  60.00  234
  2  \w    -17.00 100.00   0.50    8.15    --   10.60  82.00-150.00  234
  3  \w    -15.00 100.00   0.50    8.15    --   10.60  77.00  90.00  230
  4  \w    -20.00 100.00   0.50    8.15    --   10.60  57.00 -30.00  240
  5  \w    -79.00  36.00   0.50    8.15    --   10.60 -77.00   0.00  230
  6  \w    -79.00  41.00   0.50    8.15    --   10.60 -57.00 120.00  240
  7  \w    -17.00 100.00   0.50    8.15    --   10.60  82.00 -30.00  234
  8  \w   -100.00  17.00   0.50    8.15    --  -10.90 -82.00-120.00  234
  9  \w   -100.00  17.00   0.50    8.15    --  -10.90 -82.00 120.00  234
 10  \w   -100.00  17.00   0.50    8.15    --  -10.90 -82.00  30.00  234
 11  \w    -54.00  -1.00   0.50    8.15    --  -10.90 -77.00 -60.00  106
 12  \w    -26.00  50.00   0.50    8.15    --  -10.90  57.00-150.00  152
;
_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      -0.0482982000
_diffrn_orient_matrix_UB_12      0.0146565000
_diffrn_orient_matrix_UB_13      0.0008854000
_diffrn_orient_matrix_UB_21      -0.0025110000
_diffrn_orient_matrix_UB_22      0.0297604000
_diffrn_orient_matrix_UB_23      -0.0333799000
_diffrn_orient_matrix_UB_31      -0.0069789000
_diffrn_orient_matrix_UB_32      -0.1122807000
_diffrn_orient_matrix_UB_33      -0.0087338000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            35564
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         1.98
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.347
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29067
_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    1.405
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.299
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3191
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0346
_refine_ls_R_factor_gt           0.0315
_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^)+(0.0392P)^2^+1.3265P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0821
_refine_ls_wR_factor_ref         0.0838
_reflns_number_gt                2911
_reflns_number_total             3191
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d2ob01459a2.cif
_cod_data_source_block           k10906-myc-d
_cod_database_code               7158876
_chemical_oxdiff_formula         'C19 H21 O4 S'
_diffrn_oxdiff_digest_frames
;
01ced5631da8e27aff867c009b04ba821b000254522
;
_diffrn_oxdiff_digest_hkl
;
01bd6e6d0efb06e28eacbd398a6573a5c040e7
;
_reflns_odcompleteness_completeness 99.83
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3A), C4(H4A), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_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 1.712
_oxdiff_exptl_absorpt_empirical_full_min 0.453