Organocatalytic Asymmetric Direct α-Alkynylation of Cyclic β-Ketoesters
Thomas B. Poulsen; Luca Bernardi; José Alemán; Jacob Overgaard; Karl Anker Jørgensen; Journal of the American Chemical Society 129 (2007) 441–449; doi:10.1021/ja067289q

data_4108977
_publ_contact_author             'Overgaard, Jacob'
_publ_contact_author_email       jacobo@chem.au.dk
_publ_section_title
;
 Organocatalytic Asymmetric Direct \a-Alkynylation of Cyclic \b-Ketoesters
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              441
_journal_page_last               449
_journal_paper_doi               10.1021/ja067289q
_journal_volume                  129
_journal_year                    2007
_chemical_absolute_configuration syn
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety
;
2(C45 H49 N2 O2), 2(C6 H4 N O3), 3(C2 H3 N), 8(O)
;
_chemical_formula_sum            'C108 H115 N9 O18'
_chemical_formula_weight         1827.09
_chemical_name_systematic
;
 ?
;
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2006-10-05T15:48:27-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90.000(5)
_cell_angle_beta                 90.000(5)
_cell_angle_gamma                90.000(5)
_cell_formula_units_Z            4
_cell_length_a                   10.636(5)
_cell_length_b                   28.815(5)
_cell_length_c                   31.319(5)
_cell_measurement_reflns_used    9113
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.48
_cell_measurement_theta_min      2.32
_cell_measurement_wavelength     0.71073
_cell_volume                     9599(5)
_computing_cell_refinement       'Saint+ (Bruker-Nonius, 2006)'
_computing_data_collection       'Apex2 (Bruker-Nonius, 2006)'
_computing_data_reduction        'Saint+ (Bruker-Nonius, 2006)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR2004 (Giacovazzo et al, 2004)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 83.33
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Bruker X8 APEX-II diffractometer'
_diffrn_measurement_method       '\f-scans and \w-scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71069
_diffrn_reflns_av_R_equivalents  0.0708
_diffrn_reflns_av_unetI/netI     0.0703
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            61334
_diffrn_reflns_theta_full        23.33
_diffrn_reflns_theta_max         23.33
_diffrn_reflns_theta_min         3.42
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_description       plate
_exptl_crystal_F_000             3880
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.822
_refine_diff_density_min         -0.526
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     825
_refine_ls_number_reflns         13551
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1586
_refine_ls_R_factor_gt           0.1225
_refine_ls_shift/su_max          0.017
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1611P)^2^+42.8527P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3066
_refine_ls_wR_factor_ref         0.3288
_reflns_number_gt                9902
_reflns_number_total             13551
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja067289qrom20061011_072610.cif
_cod_data_source_block           jo40
_cod_database_code               4108977