Structure-Based Rationale for Selectivity in the Asymmetric Allylic Alkylation of Cycloalkenyl Esters Employing the Trost 'Standard Ligand' (TSL): Isolation, Analysis and Alkylation of the Monomeric form of the Cationic η3-Cyclohexenyl Complex [(η3-c-C6H9)Pd(TSL)]+
Craig P. Butts; Emane Filali; Guy C. Lloyd-Jones; Per-Ola Norrby; David A. Sale; York Schramm; Journal of the American Chemical Society 131 (2009) 9945–9957; doi:10.1021/ja8099757

data_4104708
_publ_section_title
;
 Structure-Based Rationale for Selectivity in the Asymmetric Allylic
 Alkylation of Cycloalkenyl Esters Employing the Trost 'Standard Ligand'
 (TSL): Isolation, Analysis and Alkylation of the Monomeric form of the
 Cationic \h3-Cyclohexenyl Complex [(\h3-c-C6H9)Pd(TSL)]+
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9945
_journal_page_last               9957
_journal_paper_doi               10.1021/ja8099757
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C66 H62 Br2 Cl2 D10 N2 O4 P2 Pd2, 0.5(C4 H10 O)'
_chemical_formula_sum            'C68 H67 Br2 Cl2 D10 N2 O4.5 P2 Pd2'
_chemical_formula_weight         1509.84
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           18
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_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            2
_cell_length_a                   21.123(3)
_cell_length_b                   11.8915(17)
_cell_length_c                   14.321(2)
_cell_measurement_reflns_used    16111
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      23.221
_cell_measurement_theta_min      2.391
_cell_volume                     3597.2(9)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_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      173(2)
_diffrn_detector_area_resol_mean 5.6
_diffrn_measured_fraction_theta_full 0.809
_diffrn_measured_fraction_theta_max 0.809
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_sigmaI/netI    0.0160
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            24552
_diffrn_reflns_theta_full        23.26
_diffrn_reflns_theta_max         23.26
_diffrn_reflns_theta_min         2.40
_exptl_absorpt_coefficient_mu    1.774
_exptl_absorpt_correction_T_max  0.84
_exptl_absorpt_correction_T_min  0.70
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS V2.03'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_description       block
_exptl_crystal_F_000             1522
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.929
_refine_diff_density_min         -0.178
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.008(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         4169
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0242
_refine_ls_R_factor_gt           0.0237
_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^)+(0.0418P)^2^+2.5586P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0639
_reflns_number_gt                4094
_reflns_number_total             4169
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8099757_si_002.cif
_cod_data_source_block           ef213sad
_cod_original_formula_sum        'C68 H67 Br2 Cl2 D10 N2 O4.50 P2 Pd2'
_cod_database_code               4104708