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_4124412
_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         'C26 H42 O2'
_chemical_formula_sum            'C26 H42 O2'
_chemical_formula_weight         386.60
_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                84.447(3)
_cell_angle_beta                 87.768(3)
_cell_angle_gamma                89.571(3)
_cell_formula_units_Z            2
_cell_length_a                   7.5739(3)
_cell_length_b                   10.7023(3)
_cell_length_c                   14.5550(4)
_cell_measurement_reflns_used    8865
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      72.2110
_cell_measurement_theta_min      4.8610
_cell_volume                     1173.37(7)
_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    'SIR97 (Altomare, 1999)'
_diffrn_ambient_temperature      180(2)
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.976
_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           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0256
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18064
_diffrn_reflns_theta_full        67.50
_diffrn_reflns_theta_max         72.60
_diffrn_reflns_theta_min         3.05
_exptl_absorpt_coefficient_mu    0.507
_exptl_absorpt_correction_T_max  0.952
_exptl_absorpt_correction_T_min  0.866
_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    1.094
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             428
_exptl_crystal_size_max          0.4014
_exptl_crystal_size_mid          0.1894
_exptl_crystal_size_min          0.0975
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.172
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.17(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     528
_refine_ls_number_reflns         8540
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0442
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0760P)^2^+0.1170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1219
_refine_ls_wR_factor_ref         0.1266
_reflns_number_gt                7965
_reflns_number_total             8540
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5b06281_si_003.cif
_cod_data_source_block           E9
_cod_original_cell_volume        1173.36(6)
_cod_database_code               4124412