Concise Enantioselective Synthesis of Oxygenated Steroids via Sequential Copper(II)-Catalyzed Michael Addition/Intramolecular Aldol Cyclization Reactions.
Cichowicz, Nathan R.; Kaplan, Will; Khomutnyk, Yaroslav; Bhattarai, Bijay; Sun, Zhankui; Nagorny, Pavel; Journal of the American Chemical Society 137 (2015) 14341–14348; doi:10.1021/jacs.5b08528

data_4129580
_publ_section_title
;
 Concise Enantioselective Synthesis of Oxygenated Steroids via Sequential
 Copper(II)-Catalyzed Michael Addition/Intramolecular Aldol Cyclization
 Reactions.
;
_journal_issue                   45
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14341
_journal_page_last               14348
_journal_paper_doi               10.1021/jacs.5b08528
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H28 O5'
_chemical_formula_sum            'C21 H28 O5'
_chemical_formula_weight         360.43
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P 21 21 21'
_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                   6.10720(10)
_cell_length_b                   13.8815(3)
_cell_length_c                   21.5452(15)
_cell_measurement_reflns_used    38673
_cell_measurement_temperature    85(2)
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      2.00
_cell_volume                     1826.54(14)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r12'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r12'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      85(2)
_diffrn_detector_area_resol_mean 14.629
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku Saturn944+ CCD'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_source         'micro-focus rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_sigmaI/netI    0.0188
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            51752
_diffrn_reflns_theta_full        68.23
_diffrn_reflns_theta_max         68.23
_diffrn_reflns_theta_min         3.79
_exptl_absorpt_coefficient_mu    0.750
_exptl_absorpt_correction_T_max  0.9564
_exptl_absorpt_correction_T_min  0.8644
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
    Higashi, T. (1995). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.186
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.06(13)
_refine_ls_extinction_coef       0.0061(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     242
_refine_ls_number_reflns         3337
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0279
_refine_ls_R_factor_gt           0.0278
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0398P)^2^+0.3954P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0702
_reflns_number_gt                3320
_reflns_number_total             3337
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5b08528_si_003.cif
_cod_data_source_block           zs4222
_cod_original_sg_symbol_H-M      P2(1)2(1)2(1)
_cod_database_code               4129580