Bifunctional Iminophosphorane Organocatalysts for Enantioselective Synthesis: Application to the Ketimine Nitro-Mannich Reaction
Marta G. Núñez; Alistair J. M. Farley; Darren J. Dixon; Journal of the American Chemical Society 135 (2013) 16348–16351; doi:10.1021/ja409121s

data_4121098
_publ_contact_author             'Darren Dixon'
_publ_contact_author_email       darren.dixon@chem.ox.ac.uk
_publ_section_title
;
 Bifunctional Iminophosphorane Organocatalysts for Enantioselective
 Synthesis: Application to the Ketimine Nitro-Mannich Reaction
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16348
_journal_page_last               16351
_journal_paper_doi               10.1021/ja409121s
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H38 F6 N3 O3 P1 S1'
_chemical_formula_sum            'C36 H38 F6 N3 O3 P S'
_chemical_formula_weight         737.74
_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   difmap
_atom_sites_solution_primary     other
_audit_creation_date             2012-10-10
_audit_creation_method           CRYSTALS_ver_14.52
_cell_angle_alpha                90
_cell_angle_beta                 102.5816(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8838(1)
_cell_length_b                   19.4546(2)
_cell_length_c                   15.0458(2)
_cell_measurement_reflns_used    8618
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     3680.66(7)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.057
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            98019
_diffrn_reflns_theta_full        26.912
_diffrn_reflns_theta_max         27.462
_diffrn_reflns_theta_min         5.152
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.201
_exptl_absorpt_correction_T_max  0.96
_exptl_absorpt_correction_T_min  0.63
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            clear_pale_colourless
_exptl_crystal_density_diffrn    1.331
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.58
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.37
_refine_diff_density_min         -0.27
_refine_ls_abs_structure_details 'Flack (1983), 8111 Friedel-pairs'
_refine_ls_abs_structure_Flack   -0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9649
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     902
_refine_ls_number_reflns         16705
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0391
_refine_ls_shift/su_max          0.0007460
_refine_ls_shift/su_mean         0.0000425
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.04P)^2^ + 1.60P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0891
_refine_ls_wR_factor_gt          0.0841
_refine_ls_wR_factor_ref         0.0891
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              25
_reflns_limit_k_min              -25
_reflns_limit_l_max              19
_reflns_limit_l_min              0
_reflns_number_gt                14629
_reflns_number_total             16705
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.76
_oxford_diffrn_Wilson_scale      3.84
_oxford_refine_ls_r_factor_ref   0.0489
_oxford_refine_ls_scale          0.3826(2)
_oxford_reflns_number_all        16705
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_oxford_structure_analysis_title 017djd12
_iucr_refine_instructions_details_constraints
;
BLOCK SCALE X'S, U'S 
CONT ENANTIO 
RIDE N   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  52,X'S) H   (  51,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  13,X'S) H   ( 133,X'S) H   ( 131,X'S) H   ( 132,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  21,X'S) H   ( 212,X'S) H   ( 211,X'S) H   ( 213,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
RIDE C   (  29,X'S) H   ( 292,X'S) H   ( 293,X'S) H   ( 291,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  33,X'S) H   ( 333,X'S) H   ( 331,X'S) H   ( 332,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) H   ( 342,X'S) H   ( 343,X'S) 
RIDE C   (  35,X'S) H   ( 352,X'S) H   ( 353,X'S) H   ( 351,X'S) 
RIDE N   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) 
RIDE N   (  53,X'S) H   ( 531,X'S) 
RIDE C   (  54,X'S) H   ( 541,X'S) 
RIDE C   (  55,X'S) H   ( 551,X'S) H   ( 552,X'S) 
RIDE C   (  59,X'S) H   ( 591,X'S) 
RIDE C   (  60,X'S) H   ( 601,X'S) 
RIDE C   (  63,X'S) H   ( 631,X'S) H   ( 632,X'S) H   ( 633,X'S) 
RIDE C   (  64,X'S) H   ( 641,X'S) 
RIDE C   (  65,X'S) H   ( 651,X'S) 
RIDE C   (  67,X'S) H   ( 671,X'S) 
RIDE C   (  68,X'S) H   ( 681,X'S) 
RIDE C   (  71,X'S) H   ( 711,X'S) H   ( 712,X'S) H   ( 713,X'S) 
RIDE C   (  72,X'S) H   ( 721,X'S) 
RIDE C   (  73,X'S) H   ( 731,X'S) 
RIDE C   (  75,X'S) H   ( 751,X'S) 
RIDE C   (  76,X'S) H   ( 761,X'S) 
RIDE C   (  79,X'S) H   ( 791,X'S) H   ( 792,X'S) H   ( 793,X'S) 
RIDE C   (  80,X'S) H   ( 801,X'S) 
RIDE C   (  81,X'S) H   ( 811,X'S) 
RIDE C   (  83,X'S) H   ( 831,X'S) H   ( 832,X'S) H   ( 833,X'S) 
RIDE C   (  84,X'S) H   ( 841,X'S) H   ( 843,X'S) H   ( 842,X'S) 
RIDE C   (  85,X'S) H   ( 853,X'S) H   ( 852,X'S) H   ( 851,X'S) 
RIDE N   (  86,X'S) H   ( 861,X'S) 
RIDE C   (  88,X'S) H   ( 881,X'S) 
RIDE C   (  90,X'S) H   ( 901,X'S) 
RIDE C   (  92,X'S) H   ( 921,X'S) 
END                                                                             
;
_iucr_refine_instructions_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;
_cod_data_source_file            ja409121s_si_002_2.cif
_cod_data_source_block           4b
_cod_original_sg_symbol_H-M      'P 21 '
_cod_original_formula_sum        'C36 H38 F6 N3 O3 P1 S1'
_cod_database_code               4121098