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_4121097
_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         'C38 H34 F6 N3 O3 P1 S1'
_chemical_formula_sum            'C38 H34 F6 N3 O3 P S'
_chemical_formula_weight         757.73
_space_group_IT_number           154
_symmetry_cell_setting           trigonal
_symmetry_space_group_name_Hall  'P 32 2"'
_symmetry_space_group_name_H-M   'P 32 2 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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.8761(1)
_cell_length_b                   22.8761(1)
_cell_length_c                   14.2626(1)
_cell_measurement_reflns_used    9785
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     6463.88(6)
_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 0.990
_diffrn_measured_fraction_theta_max 0.990
_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  0.062
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            177140
_diffrn_reflns_theta_full        26.913
_diffrn_reflns_theta_max         27.463
_diffrn_reflns_theta_min         5.146
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.173
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.88
_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    1.168
_exptl_crystal_description       block
_exptl_crystal_F_000             2352
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.34
_platon_squeeze_details
;
The discrete Fourier transform of the void region were treated as 
contributions to the A and B parts of the calculated structure factors.
;
_refine_diff_density_max         0.25
_refine_diff_density_min         -0.24
_refine_ls_abs_structure_details 'Flack (1983), 4540 Friedel-pairs'
_refine_ls_abs_structure_Flack   -0.076(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         9787
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0420
_refine_ls_shift/su_max          0.0010312
_refine_ls_shift/su_mean         0.0000351
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 41.1 68.1 40.7 16.4 3.54 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1060
_refine_ls_wR_factor_gt          0.1020
_refine_ls_wR_factor_ref         0.1060
_reflns_limit_h_max              14
_reflns_limit_h_min              -29
_reflns_limit_k_max              29
_reflns_limit_k_min              0
_reflns_limit_l_max              18
_reflns_limit_l_min              0
_reflns_number_gt                9025
_reflns_number_total             9789
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.89
_oxford_diffrn_Wilson_scale      26.47
_oxford_refine_ls_r_factor_ref   0.0463
_oxford_refine_ls_scale          0.3040(2)
_oxford_reflns_number_all        9788
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_oxford_structure_analysis_title 006DJD12
_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   ( 132,X'S) H   ( 131,X'S) H   ( 133,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   ( 211,X'S) H   ( 212,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   ( 291,X'S) H   ( 293,X'S) H   ( 292,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   ( 331,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE N   (  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 C   (  44,X'S) H   ( 441,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_1.cif
_cod_data_source_block           4c
_cod_original_sg_symbol_H-M      'P 32 2 1 '
_cod_original_formula_sum        'C38 H34 F6 N3 O3 P1 S1'
_cod_database_code               4121097