Enantioselective desymmetrization of diphenylphosphinamides via (-)-sparteine-mediated ortho-lithiation. Synthesis of P-chiral ligands.
Popovici, Cristinel; Oña-Burgos, Pascual; Fernández, Ignacio; Roces, Laura; García-Granda, Santiago; Iglesias, María José; López Ortiz, Fernando; Organic letters 12 (2010) 428–431; doi:10.1021/ol902545q

data_1503354
_publ_section_title
;
 Enantioselective desymmetrization of diphenylphosphinamides via
 (-)-sparteine-mediated ortho-lithiation. Synthesis of P-chiral ligands.
;
_journal_issue                   3
_journal_name_full               'Organic letters'
_journal_page_first              428
_journal_page_last               431
_journal_paper_doi               10.1021/ol902545q
_journal_volume                  12
_journal_year                    2010
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C44 H58 N4 O2 P2'
_chemical_formula_sum            'C44 H58 N4 O2 P2'
_chemical_formula_weight         736.88
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_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_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4
_audit_creation_date             2009-10-23T12:50:11-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 103.2440(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.44170(10)
_cell_length_b                   16.4362(2)
_cell_length_c                   16.0375(2)
_cell_measurement_reflns_used    6361
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.8143
_cell_measurement_theta_min      3.901
_cell_measurement_wavelength     1.54184
_cell_volume                     2166.01(5)
_computing_cell_refinement
;
        CrysAlisPro, Oxford Diffraction Ltd.,
        Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
        (compiled Sep 15 2009,11:49:04)
;
_computing_data_collection
;
        CrysAlisPro, Oxford Diffraction Ltd.,
        Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
        (compiled Sep 15 2009,11:49:04)
;
_computing_data_reduction
;
        CrysAlisPro, Oxford Diffraction Ltd.,
        Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
        (compiled Sep 15 2009,11:49:04)
;
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'DIRDIF99 (Beurskens et al, 1999)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0827
_diffrn_measured_fraction_theta_full 0.957
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0081508984
_diffrn_orient_matrix_UB_12      -0.091340434
_diffrn_orient_matrix_UB_13      0.0201284329
_diffrn_orient_matrix_UB_21      -0.0462969428
_diffrn_orient_matrix_UB_22      -0.0189873472
_diffrn_orient_matrix_UB_23      -0.0965722102
_diffrn_orient_matrix_UB_31      0.1815251089
_diffrn_orient_matrix_UB_32      -0.0088903377
_diffrn_orient_matrix_UB_33      -0.000390943
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.024
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11547
_diffrn_reflns_theta_full        66.86
_diffrn_reflns_theta_max         66.86
_diffrn_reflns_theta_min         3.91
_exptl_absorpt_coefficient_mu    1.205
_exptl_absorpt_correction_T_max  0.923
_exptl_absorpt_correction_T_min  0.842
_exptl_absorpt_correction_type   refdelf
_exptl_absorpt_process_details
;
Parkin S,Moezzi B & Hope H, (1995) J. Appl. Cryst. 28, 53-56
Cubic fit to sin(theta)/lambda - 24 parameters
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.13
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.195
_refine_diff_density_min         -0.214
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.001(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         6768
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0379
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0634P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.1
_reflns_number_gt                5512
_reflns_number_total             6768
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol902545q_si_003.cif
_cod_data_source_block           c257
_cod_database_code               1503354