Bismuth(III) Triflate-Catalyzed Direct Conversion of Corticosteroids into Highly Functionalized 17-Ketosteroids by Cleavage of the C17-Dihydroxyacetone Side Chain
Rui M. A. Pinto; Jorge A. R. Salvador; Christophe Le Roux; José A. Paixão; Journal of Organic Chemistry 74 (2009) 8488–8491; doi:10.1021/jo9018478

data_4024969
_publ_section_title
;
Bismuth(III) Triflate-Catalyzed Direct Conversion of Corticosteroids into
Highly Functionalized 17-Ketosteroids by Cleavage of
the C17-Dihydroxyacetone Side Chain
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              8488
_journal_page_last               8491
_journal_paper_doi               10.1021/jo9018478
_journal_volume                  74
_journal_year                    2009
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C20 H24 O3'
_chemical_formula_sum            'C20 H24 O3'
_chemical_formula_weight         312.39
_chemical_name_systematic
; 
 9\b,11\b-epoxy-16\b-methylandrost-1,4-diene-3,17-dione
;
_space_group_IT_number           1
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                81.061(2)
_cell_angle_beta                 75.932(2)
_cell_angle_gamma                89.738(2)
_cell_formula_units_Z            2
_cell_length_a                   7.8454(2)
_cell_length_b                   9.7552(3)
_cell_length_c                   11.3075(3)
_cell_measurement_reflns_used    4834
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.8779
_cell_measurement_theta_min      2.5169
_cell_volume                     828.75(4)
_computing_cell_refinement       'SAINT (Bruker, 2003)'
_computing_data_collection       'SMART (Bruker, 2003)'
_computing_data_reduction        SAINT
_computing_molecular_graphics    'PLATON (Spek, 2003)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD area-detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_sigmaI/netI    0.0408
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_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            16806
_diffrn_reflns_theta_full        27.99
_diffrn_reflns_theta_max         27.99
_diffrn_reflns_theta_min         1.88
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  0.99
_exptl_absorpt_correction_T_min  0.953
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS;  Sheldrick, 2000)'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.395
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.8(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    riding
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         3969
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0864
_refine_ls_R_factor_gt           0.0668
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0635P)^2^+0.2168P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1395
_refine_ls_wR_factor_ref         0.1493
_reflns_number_gt                3126
_reflns_number_total             3969
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            jo9018478_si_003.cif
_cod_data_source_block           rpc32
_cod_database_code               4024969