Diastereodivergent Hydroxyfluorination of Cyclic and Acyclic Allylic Amines: Synthesis of 4-Deoxy-4-fluorophytosphingosines
Alexander J. Cresswell; Stephen G. Davies; James A. Lee; Melloney J. Morris; Paul M. Roberts; James E. Thomson; Journal of Organic Chemistry 77 (2012) 7262–7281; doi:10.1021/jo301056r

data_4027435
_publ_contact_author             'Stephen G. Davies'
_publ_contact_author_email       steve.davies@chem.ox.ac.uk
_publ_contact_author_fax         '+44 1865 275633'
_publ_contact_author_phone       '+44 1865 275695'
_publ_section_title
;
 Diastereodivergent Hydroxyfluorination of Cyclic and Acyclic Allylic
 Amines: Synthesis of 4-Deoxy-4-fluorophytosphingosines
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              7262
_journal_page_last               7281
_journal_paper_doi               10.1021/jo301056r
_journal_volume                  77
_journal_year                    2012
_chemical_formula_moiety         'C20 H24 B1 Cl3 F5 N1 O1'
_chemical_formula_sum            'C20 H24 B Cl3 F5 N O'
_chemical_formula_weight         506.58
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 110.5782(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0623(3)
_cell_length_b                   9.4128(2)
_cell_length_c                   17.4909(4)
_cell_measurement_reflns_used    5191
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     2321.60(9)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 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 0.992
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.021
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            8925
_diffrn_reflns_theta_full        26.948
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_min         5.113
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.447
_exptl_absorpt_correction_T_max  0.96
_exptl_absorpt_correction_T_min  0.96
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_description       prism
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.230
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.080
_refine_diff_density_max         1.63
_refine_diff_density_min         -1.07
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.0157
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5283
_refine_ls_number_restraints     48
_refine_ls_R_factor_all          0.0886
_refine_ls_R_factor_gt           0.0700
_refine_ls_shift/su_max          0.0001686
_refine_ls_shift/su_mean         0.0000160
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
Method= Modified Sheldrick
w=1/[\s^2^(F^2^) + ( 0.08P)^2^ + 4.08P]
,where P=(max(Fo^2^,0) + 2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1855
_refine_ls_wR_factor_gt          0.1724
_refine_ls_wR_factor_ref         0.1855
_reflns_limit_h_max              18
_reflns_limit_h_min              -19
_reflns_limit_k_max              12
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              0
_reflns_number_gt                4083
_reflns_number_total             5283
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   3.38
_oxford_diffrn_Wilson_scale      4.05
_oxford_refine_ls_r_factor_ref   0.0886
_oxford_refine_ls_scale          0.581(2)
_oxford_reflns_number_all        5283
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_cod_data_source_file            jo301056r_si_001_04.cif
_cod_data_source_block           25.HBF4
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_original_formula_sum        'C20 H24 B1 Cl3 F5 N1 O1'
_cod_database_code               4027435