Chiral Primary Amine Catalyzed Asymmetric Michael Addition of Malononitrile to α-Substituted Vinyl Ketone.
Fu, Niankai; Zhang, Long; Luo, Sanzhong; Organic letters 17 (2015) 382–385; doi:10.1021/ol503566a

data_1518618
_publ_section_title
;
 Chiral Primary Amine Catalyzed Asymmetric Michael Addition of
 Malononitrile to \a-Substituted Vinyl Ketone.
;
_journal_issue                   2
_journal_name_full               'Organic letters'
_journal_page_first              382
_journal_page_last               385
_journal_paper_doi               10.1021/ol503566a
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H17 Br N2 O'
_chemical_formula_sum            'C20 H17 Br N2 O'
_chemical_formula_weight         381.26
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-09-23
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                76.557(12)
_cell_angle_beta                 73.136(13)
_cell_angle_gamma                64.754(10)
_cell_formula_units_Z            2
_cell_length_a                   9.8359(19)
_cell_length_b                   10.161(2)
_cell_length_c                   10.307(2)
_cell_measurement_reflns_used    3917
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      33.0213
_cell_measurement_theta_min      2.2338
_cell_volume                     884.6(3)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0867
_diffrn_orient_matrix_UB_12      -0.0680
_diffrn_orient_matrix_UB_13      0.0336
_diffrn_orient_matrix_UB_21      0.0844
_diffrn_orient_matrix_UB_22      -0.0012
_diffrn_orient_matrix_UB_23      0.0701
_diffrn_orient_matrix_UB_31      -0.0347
_diffrn_orient_matrix_UB_32      0.0933
_diffrn_orient_matrix_UB_33      0.0233
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14811
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.472
_diffrn_reflns_theta_min         3.240
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.332
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7439
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.431
_exptl_crystal_description       block
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.340
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 3293 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.009(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     435
_refine_ls_number_reflns         7894
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0320
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0319P)^2^+0.1081P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0718
_refine_ls_wR_factor_ref         0.0739
_reflns_Friedel_coverage         0.956
_reflns_Friedel_fraction_full    0.959
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                7490
_reflns_number_total             7894
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol503566a_si_002.cif
_cod_data_source_block           sa3636
_cod_database_code               1518618
_shelxl_version_number           2013-4
_diffrn_number_total             4040
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1A(H1A), C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C10A(H10A,H10B), C14A(H14A,H14B), C10(H10C,H10D), C14(H14C,H14D)
2.c Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C8A(H8A), C16A(H16A), C17A(H17A),
 C19A(H19A), C20A(H20A), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C16(H16),
 C17(H17), C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C9A(H9AA,H9AB,H9AC), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              80442
_shelx_hkl_checksum              22022