Diastereoselective and Enantioselective Synthesis of Unsymmetric β,β-Diaryl-α-Amino Acid Esters via Organocatalytic 1,6-Conjugate Addition of para-Quinone Methides.
Zhang, Xiang-Zhi; Deng, Yu-Hua; Yan, Xu; Yu, Ke-Yin; Wang, Fang-Xin; Ma, Xiao-Yan; Fan, Chun-An; The Journal of organic chemistry 81 (2016) 5655–5662; doi:10.1021/acs.joc.6b00390

data_4036732
_publ_section_title
;
 Diastereoselective and Enantioselective Synthesis of Unsymmetric
 \b,\b-Diaryl-\a-Amino Acid Esters via Organocatalytic 1,6-Conjugate
 Addition of para-Quinone Methides.
;
_journal_issue                   13
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5655
_journal_page_last               5662
_journal_paper_doi               10.1021/acs.joc.6b00390
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H38 Br N O3'
_chemical_formula_sum            'C27 H38 Br N O3'
_chemical_formula_weight         504.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.5696(7)
_cell_length_b                   10.6323(6)
_cell_length_c                   26.1335(14)
_cell_measurement_reflns_used    4344
_cell_measurement_temperature    300.79(10)
_cell_measurement_theta_max      70.0240
_cell_measurement_theta_min      4.5780
_cell_volume                     2659.0(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.79(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega   48.00  106.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  -90.0000 58

  2 omega  100.00  153.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -180.0000 53

  3 omega  121.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -150.0000 57

  4 omega  115.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000 -120.0000 62

  5 omega   87.00  127.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000  -60.0000 40

  6 omega   54.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -180.0000 35

  7 omega   40.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -120.0000 53

  8 omega   57.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000  -60.0000 26

  9 omega   36.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000  -60.0000 57

 10 omega   36.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000 -180.0000 30

 11 omega   32.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  -90.0000 73

 12 omega   42.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000  120.0000 60

 13 omega   33.00  112.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000   90.0000 79

 14 omega   23.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   30.0000 45

 15 omega   34.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000 -120.0000 40

 16 omega  -19.00   36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000    0.0000 55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1386481000
_diffrn_orient_matrix_UB_12      -0.0299050000
_diffrn_orient_matrix_UB_13      0.0273319000
_diffrn_orient_matrix_UB_21      -0.0572564000
_diffrn_orient_matrix_UB_22      -0.0590758000
_diffrn_orient_matrix_UB_23      -0.0496389000
_diffrn_orient_matrix_UB_31      0.0584773000
_diffrn_orient_matrix_UB_32      -0.1288161000
_diffrn_orient_matrix_UB_33      0.0163202000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            9254
_diffrn_reflns_theta_full        70.11
_diffrn_reflns_theta_max         70.11
_diffrn_reflns_theta_min         3.38
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.307
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76988
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.27
_refine_diff_density_max         0.413
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.04(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4927
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0419
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0566P)^2^+0.6845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1173
_reflns_number_gt                4392
_reflns_number_total             4927
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo6b00390_si_001.cif
_cod_data_source_block           zhangxzh0720_2
_cod_database_code               4036732
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H1B-N1
 0.86 with sigma of 0.01
 N1-H1A
 0.86 with sigma of 0.01
 O1-H1
 0.86 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C15(H15), C22(H22)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C17(H17), C19(H19), C20(H20), C21(H21)
3.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C)
;
_olex2_date_sample_data_collection 2015-07-20
_olex2_submission_special_instructions 'No special instructions were received'