Mechanism and Enantioselectivity in Palladium-Catalyzed Conjugate Addition of Arylboronic Acids to β-Substituted Cyclic Enones: Insights from Computation and Experiment
Jeffrey C. Holder; Lufeng Zou; Alexander N. Marziale; Peng Liu; Yu Lan; Michele Gatti; Kotaro Kikushima; K. N. Houk; Brian M. Stoltz; Journal of the American Chemical Society 135 (2013) 14996–15007; doi:10.1021/ja401713g

data_4120910
_publ_section_title
;
 Mechanism and Enantioselectivity in Palladium-Catalyzed Conjugate
 Addition of Arylboronic Acids to \b-Substituted Cyclic Enones: Insights
 from Computation and Experiment
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14996
_journal_page_last               15007
_journal_paper_doi               10.1021/ja401713g
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_sum            'C17.8 H20.83 I1.03 N2 O Pd'
_chemical_formula_weight         516.47
_chemical_name_systematic
; 
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 101.240(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.4571(12)
_cell_length_b                   9.9004(6)
_cell_length_c                   10.5480(7)
_cell_measurement_reflns_used    9945
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.12
_cell_measurement_theta_min      2.25
_cell_volume                     1890.5(2)
_computing_cell_refinement       'SAINT 8.27B (Bruker-AXS, 2011)'
_computing_data_collection       'APEX2 v2013.2.0 (Bruker-AXS, 2013)'
_computing_data_reduction        'SAINT 8.27B (Bruker-AXS, 2011)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            24103
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.600
_diffrn_reflns_theta_min         1.968
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    2.677
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_correction_T_min  0.665
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.815
_exptl_crystal_description       Needle
_exptl_crystal_F_000             1002
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.050
_refine_diff_density_max         0.568
_refine_diff_density_min         -0.578
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
; 
 Flack x determined using 2410 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.023(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         5762
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0269
_refine_ls_R_factor_gt           0.0226
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
; 
 w=1/[\s^2^(Fo^2^)+(0.0152P)^2^] 
 where P=(Fo^2^+2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0403
_refine_ls_wR_factor_ref         0.0414
_reflns_Friedel_coverage         0.891
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                5355
_reflns_number_total             5762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja401713g_si_003.cif
_cod_data_source_block           anm02
_cod_original_formula_sum        'C17.80 H20.83 I1.03 N2 O Pd'
_cod_database_code               4120910
_shelx_estimated_absorpt_t_min   0.690
_shelx_estimated_absorpt_t_max   0.878
_shelxl_version_number           2013-2
_shelx_res_checksum              4951