Oxygen Donor-Mediated Equilibration of Diastereomeric Alkene-Palladium(II) Intermediates in Enantioselective Desymmetrizing Heck Cyclizations
Axel B. Machotta; Bernd F. Straub; Martin Oestreich; Journal of the American Chemical Society 129 (2007) 13455–13463; doi:10.1021/ja072571y

data_4110118
_publ_section_title
;
 Oxygen Donor-Mediated Equilibration of Diastereomeric
 Alkene-Palladium(II) Intermediates in Enantioselective Desymmetrizing
 Heck Cyclizations
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13455
_journal_page_last               13463
_journal_paper_doi               10.1021/ja072571y
_journal_volume                  129
_journal_year                    2007
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H24 Br2 O5'
_chemical_formula_sum            'C27 H24 Br2 O5'
_chemical_formula_weight         588.28
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_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_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                   6.2677(2)
_cell_length_b                   11.0850(4)
_cell_length_c                   34.9451(15)
_cell_measurement_reflns_used    14385
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.485
_cell_measurement_theta_min      0.998
_cell_volume                     2427.90(16)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction
'HKL Denzo and Scalepack (Otwinowski & Minor 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SIR-97 (Giacovazzo, 1997)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       '95mm CCD camera on \k-goniostat'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       CCD
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_diffrn_radiation_source         'long-fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0742
_diffrn_reflns_av_sigmaI/netI    0.1198
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            13850
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         27.44
_diffrn_reflns_theta_min         1.17
_exptl_absorpt_coefficient_mu    3.375
_exptl_absorpt_correction_T_max  0.824
_exptl_absorpt_correction_T_min  0.623
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
multi-scan from symmetry-related measurements 
 Sortav (Blessing 1995)
;
_exptl_crystal_colour            white
_exptl_crystal_density_diffrn    1.609
_exptl_crystal_description       needle
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.452
_refine_diff_density_min         -0.548
_refine_diff_density_rms         0.114
_refine_ls_abs_structure_details
'Flack H D (1983), Acta Cryst. A39, 876-881, 2231 Friedel pairs'
_refine_ls_abs_structure_Flack   -0.019(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.882
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5419
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.882
_refine_ls_R_factor_all          0.0871
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0005P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0506
_refine_ls_wR_factor_ref         0.0588
_reflns_number_gt                3473
_reflns_number_total             5419
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja072571ysi20070710_025722.cif
_cod_data_source_block           mk373l
_cod_original_sg_symbol_H-M      'P 21 21 21 '
_cod_database_code               4110118