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_4120688
_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            'C49 H47 Br Cl4 O2 P2 Pd'
_chemical_formula_weight         1057.92
_chemical_name_systematic
; 
 ? 
;
_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                   9.4609(7)
_cell_length_b                   21.4594(17)
_cell_length_c                   22.4518(17)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    140(2)
_cell_measurement_theta_max      31.50
_cell_measurement_theta_min      2.35
_cell_volume                     4558.3(6)
_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, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      140(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_sigmaI/netI    0.0676
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            48529
_diffrn_reflns_theta_full        31.62
_diffrn_reflns_theta_max         31.62
_diffrn_reflns_theta_min         1.31
_exptl_absorpt_coefficient_mu    1.628
_exptl_absorpt_correction_T_max  0.7807
_exptl_absorpt_correction_T_min  0.6769
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2144
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.969
_refine_diff_density_min         -0.979
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.025(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     533
_refine_ls_number_reflns         15266
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0436
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0506P)^2^+1.8582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1082
_reflns_number_gt                12845
_reflns_number_total             15266
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja410707q_si_005.cif
_cod_data_source_block           mo_dm13148_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Orthorhombic' changed to
'orthorhombic' 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)2(1)2(1)
_cod_database_code               4120688