Copper(I)-Catalyzed Asymmetric Desymmetrization: Synthesis of Five-Membered-Ring Compounds Containing All-Carbon Quaternary Stereocenters
Kohsuke Aikawa; Tatsuya Okamoto; Koichi Mikami; Journal of the American Chemical Society 134 (2012) 10329–10332; doi:10.1021/ja3032345

data_4118124
_publ_contact_author_address
;
O-okayama, Meguro-ku, Tokyo 152-8552 (Japan)
;
_publ_contact_author_email       aikawa.k.aa@m.titech.ac.jp
_publ_contact_author_fax         (+81)3-5734-2776
_publ_contact_author_name        'Kohsuke Aikawa'
_publ_contact_author_phone       (+81)3-5734-2776
_publ_section_title
;
 Copper(I)-Catalyzed Asymmetric Desymmetrization: Synthesis of
 Five-Membered-Ring Compounds Containing All-Carbon Quaternary
 Stereocenters
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10329
_journal_page_last               10332
_journal_paper_doi               10.1021/ja3032345
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_sum            'C23 H25 Br O4'
_chemical_formula_weight         445.34
_chemical_name_common
;
(2S,4R,5S)-2-((benzyloxy)methyl)-4-((S)-(4-bromophenyl)
(hydroxy)methyl)-5-ethyl-2-methylcyclopentane-1,3-dione 
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_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                 104.7050(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   12.1259(13)
_cell_length_b                   6.5546(7)
_cell_length_c                   13.8267(15)
_cell_measurement_reflns_used    1914
_cell_measurement_temperature    93
_cell_measurement_theta_max      26.52
_cell_measurement_theta_min      2.58
_cell_volume                     1063.0(2)
_computing_cell_refinement       'Bruker APEX2 (Bruker AXS, 2010)'
_computing_data_collection       'Bruker APEX2 (Bruker AXS, 2010)'
_computing_data_reduction        'Bruker SAINT (Bruker AXS, 2004)'
_computing_molecular_graphics    'Brukre SHELXTL (Bruker AXS,2008)'
_computing_publication_material  'Bruker XCIF (Bruker AXS, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      93
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEXII CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  'Bruker Helios multilayer confocal mirror'
_diffrn_radiation_source         'Bruker TXS fine-focus rotating anode'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0647
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            2663
_diffrn_reflns_theta_full        27.60
_diffrn_reflns_theta_max         27.60
_diffrn_reflns_theta_min         1.52
_exptl_absorpt_coefficient_mu    1.959
_exptl_absorpt_correction_T_max  0.8590
_exptl_absorpt_correction_T_min  0.4409
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS Sheldrick 1996
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       column
_exptl_crystal_F_000             460
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.506
_refine_diff_density_min         -0.362
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.075(14)
_refine_ls_extinction_coef       0.015(4)
_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   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         2663
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0387
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0500P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0810
_refine_ls_wR_factor_ref         0.1008
_reflns_number_gt                2448
_reflns_number_total             2663
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja3032345_si_002.cif
_cod_data_source_block           OBn
_cod_original_sg_symbol_H-M      'P 1 21 1 '
_cod_database_code               4118124