Ring-Opening Hydrofluorination of 2,3- and 3,4-Epoxy Amines by HBF4.OEt2: Application to the Asymmetric Synthesis of (S,S)-3-Deoxy-3-fluorosafingol
Alexander J. Cresswell; Stephen G. Davies; James A. Lee; Melloney J. Morris; Paul M. Roberts; James E. Thomson; Journal of Organic Chemistry 76 (2011) 4617–4627; doi:10.1021/jo200517w

data_4026368
_publ_contact_author_address
;Department of Chemistry
Chemistry Research Laboratory
University of Oxford
Mansfield Road
Oxford
OX1 3TA
U.K.
;
_publ_contact_author_email       steve.davies@chem.ox.ac.uk
_publ_contact_author_fax         '+44 1865 275633'
_publ_contact_author_name        'Stephen G. Davies'
_publ_contact_author_phone       '+44 1865 276595'
_publ_section_title
;
 Ring-Opening Hydrofluorination of 2,3- and 3,4-Epoxy Amines by HBF4.OEt2:
 Application to the Asymmetric Synthesis of (S,S)-3-Deoxy-3-fluorosafingol
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              4617
_journal_page_last               4627
_journal_paper_doi               10.1021/jo200517w
_journal_volume                  76
_journal_year                    2011
_chemical_formula_moiety         'C20 H24 F1 N1 O1'
_chemical_formula_sum            'C20 H24 F N O'
_chemical_formula_weight         313.41
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             09-12-03
_audit_creation_method           CRYSTALS_ver_12.85
_cell_angle_alpha                85.9331(12)
_cell_angle_beta                 84.5582(12)
_cell_angle_gamma                87.1641(16)
_cell_formula_units_Z            2
_cell_length_a                   5.69120(10)
_cell_length_b                   11.1440(3)
_cell_length_c                   12.9653(4)
_cell_measurement_reflns_used    3267
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     815.77(4)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 1997-2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'Nonius KappaCCD'
_diffrn_measurement_device_type  Area
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.032
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5938
_diffrn_reflns_theta_full        26.341
_diffrn_reflns_theta_max         27.438
_diffrn_reflns_theta_min         5.253
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  0.99
_exptl_absorpt_correction_T_min  0.99
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       plate
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.22
_refine_diff_density_min         -0.17
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.1348
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         2331
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0480
_refine_ls_shift/su_max          0.000275
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 0.397 0.170 0.128 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0830
_refine_ls_wR_factor_gt          0.0493
_refine_ls_wR_factor_ref         0.0460
_reflns_limit_h_max              7
_reflns_limit_h_min              -7
_reflns_limit_k_max              14
_reflns_limit_k_min              -14
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                2540
_reflns_number_total             3696
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.36
_oxford_diffrn_Wilson_scale      2.03
_oxford_refine_ls_r_factor_ref   0.0429
_oxford_refine_ls_scale          0.6890(14)
_oxford_reflns_number_all        3696
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_cod_data_source_file            jo200517w_si_001.cif
_cod_data_source_block           1
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C20 H24 F1 N1 O1'
_cod_database_code               4026368