Spiroketal-based diphosphine ligands in pd-catalyzed asymmetric allylic amination of morita-baylis-hillman adducts: exceptionally high efficiency and new mechanism.
Wang, Xiaoming; Guo, Peihua; Han, Zhaobin; Wang, Xubin; Wang, Zheng; Ding, Kuiling; Journal of the American Chemical Society 136 (2014) 405–411; doi:10.1021/ja410707q

data_4120685
_publ_section_title
;
 Spiroketal-based diphosphine ligands in pd-catalyzed asymmetric allylic
 amination of morita-baylis-hillman adducts: exceptionally high efficiency
 and new mechanism.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              405
_journal_page_last               411
_journal_paper_doi               10.1021/ja410707q
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_sum            'C56 H55 Cl O8 P2 Pd'
_chemical_formula_weight         1059.79
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_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                 113.629(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.3703(5)
_cell_length_b                   18.4887(10)
_cell_length_c                   13.6456(8)
_cell_measurement_reflns_used    1972
_cell_measurement_temperature    143(2)
_cell_measurement_theta_max      80.660
_cell_measurement_theta_min      8.488
_cell_volume                     2628.1(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_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      416(2)
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.2043
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            7133
_diffrn_reflns_theta_full        65.50
_diffrn_reflns_theta_max         65.50
_diffrn_reflns_theta_min         4.27
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.315
_exptl_absorpt_correction_T_max  0.7546
_exptl_absorpt_correction_T_min  0.3465
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             1096
_exptl_crystal_size_max          0.165
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.034
_platon_squeeze_details
;
;
_refine_diff_density_max         0.971
_refine_diff_density_min         -0.804
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.020(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.932
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         7133
_refine_ls_number_restraints     416
_refine_ls_restrained_S_all      0.924
_refine_ls_R_factor_all          0.1837
_refine_ls_R_factor_gt           0.0896
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1331P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2273
_refine_ls_wR_factor_ref         0.2672
_reflns_number_gt                3220
_reflns_number_total             7133
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja410707q_si_006.cif
_cod_data_source_block           cu_dm13230_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to
/usr/data/users/saulius/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_sg_symbol_H-M      P2(1)
_cod_database_code               4120685