Highly Enantioselective Copper-Catalyzed Alkylation of β-Ketoesters and Subsequent Cyclization to Spirolactones/Bi-spirolactones
Qing-Hai Deng; Hubert Wadepohl; Lutz H. Gade; Journal of the American Chemical Society 134 (2012) 2946–2949; doi:10.1021/ja211859w

data_4117492
_publ_section_title
;
 Highly Enantioselective Copper-Catalyzed Alkylation of \b-Ketoesters and
 Subsequent Cyclization to Spirolactones/Bi-spirolactones
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2946
_journal_page_last               2949
_journal_paper_doi               10.1021/ja211859w
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_sum            'C31 H29 Cu N3 O5'
_chemical_formula_weight         587.11
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_qd6
_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                   10.592(5)
_cell_length_b                   13.611(7)
_cell_length_c                   18.762(9)
_cell_measurement_reflns_used    8116
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.93
_cell_measurement_theta_min      2.44
_cell_volume                     2705(2)
_computing_cell_refinement
;
SAINT (Bruker AXS, 1997-2008). Includes estimated systematic errors
 of the unit cell constants from Monte Carlo simulations.
;
_computing_data_collection       'SMART-5.631 (Bruker AXS, 2003)'
_computing_data_reduction
'SAINT (Bruker AXS, 1997-2008); SADABS (Bruker AXS, 2008)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.19
_diffrn_detector_type            CCD-PXL-KAF2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker AXS Smart 1000'
_diffrn_measurement_method       '\f- and \w-scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0542
_diffrn_reflns_av_sigmaI/netI    0.0346
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            66656
_diffrn_reflns_theta_full        31.51
_diffrn_reflns_theta_max         31.51
_diffrn_reflns_theta_min         1.85
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.854
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6703
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements (Blessing 1995)
SADABS (Sheldrick & Bruker AXS, 2004-2008)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       needle
_exptl_crystal_F_000             1220
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.021(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     364
_refine_ls_number_reflns         8905
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0344
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0387P)^2^+0.7905P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0754
_refine_ls_wR_factor_ref         0.0798
_reflns_number_gt                7928
_reflns_number_total             8905
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja211859w_si_002.cif
_cod_data_source_block           ga_qd6
_cod_database_code               4117492
_audit_block_refno               1338