Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols for the Stereoselective Construction of C(20) in Steroid Side Chains: Scope and Topological Diversification.
Li, Houhua; Mazet, Clément; Journal of the American Chemical Society  (2015) 150811163019004–; doi:10.1021/jacs.5b06281

data_4124409
_publ_section_title
;
 Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols
 for the Stereoselective Construction of C(20) in Steroid Side Chains:
 Scope and Topological Diversification.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              150811163019004
_journal_paper_doi               10.1021/jacs.5b06281
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H38 O2, 1.5(H2 O)'
_chemical_formula_sum            'C28 H41 O3.5'
_chemical_formula_weight         433.61
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   31.0988(12)
_cell_length_b                   9.8634(3)
_cell_length_c                   7.9792(2)
_cell_measurement_reflns_used    3071
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      73.3610
_cell_measurement_theta_min      4.6870
_cell_volume                     2447.54(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Ortep 3 (Farrugia, 1997)'
_computing_publication_material  ShelX_Acta
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      180(2)
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0498
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            8300
_diffrn_reflns_theta_full        67.50
_diffrn_reflns_theta_max         73.52
_diffrn_reflns_theta_min         4.70
_exptl_absorpt_coefficient_mu    0.590
_exptl_absorpt_correction_T_max  0.990
_exptl_absorpt_correction_T_min  0.846
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             948
_exptl_crystal_size_max          0.4775
_exptl_crystal_size_mid          0.2917
_exptl_crystal_size_min          0.0164
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.201
_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   0.4(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         4793
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0663
_refine_ls_R_factor_gt           0.0523
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0599P)^2^+0.1426P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1318
_refine_ls_wR_factor_ref         0.1395
_reflns_number_gt                3963
_reflns_number_total             4793
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5b06281_si_003.cif
_cod_data_source_block           Z7a
_cod_original_cell_volume        2447.53(14)
_cod_original_formula_sum        'C28 H41 O3.50'
_cod_database_code               4124409