Divergent and Scalable Synthesis of α-Hydroxy/Keto-β-amino Acid Analogues by the Catalytic Enantioselective Addition of Glyoxylate Cyanohydrin to Imines
Nanjo, Takeshi; Zhang, Xuan; Tokuhiro, Yusuke; Takemoto, Yoshiji; ACS Catalysis  (2019) 10087–; doi:10.1021/acscatal.9b03394

data_4514899
_publ_section_title
;
 Divergent and Scalable Synthesis of \a-Hydroxy/Keto-\b-amino Acid
 Analogues by the Catalytic Enantioselective Addition of Glyoxylate
 Cyanohydrin to Imines
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10087
_journal_paper_doi               10.1021/acscatal.9b03394
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C27 H32 N2 O7'
_chemical_formula_sum            'C27 H32 N2 O7'
_chemical_formula_weight         496.54
_chemical_melting_point          416
_chemical_name_systematic
'tert-butyl (2S,3R)-2-(((benzyloxy)carbonyl)oxy)-3-((tert-butoxycarbonyl)amino)-2-cyano-3-phenylpropanoate'
_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_Hall           'P 31'
_space_group_name_H-M_alt        'P 31'
_symmetry_space_group_name_Hall  'P 31'
_symmetry_space_group_name_H-M   'P 31'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-02 deposited with the CCDC.    2019-05-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   19.4343(4)
_cell_length_b                   19.4343(4)
_cell_length_c                   6.0779(2)
_cell_measurement_reflns_used    6916
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.9570
_cell_measurement_theta_min      2.6020
_cell_volume                     1988.03(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -134.00 -38.00   0.50    0.76    --  -45.50  60.00  30.00  192
  2  \w   -134.00 -38.00   0.50    0.76    --  -45.50  60.00 150.00  192
  3  \w   -190.00 -37.00   0.50    4.66    -- -101.50  59.00 161.95  306
  4  \w   -190.00 -37.00   0.50    4.66    -- -101.50  59.00  59.79  306
  5  \w   -190.00 -38.00   0.50    4.66    -- -101.50  60.00 175.49  304
  6  \w   -190.00 -13.00   0.50    4.66    -- -101.50  20.00  30.00  354
  7  \w   -134.00 -92.00   0.50    0.76    --  -45.50  41.00  -6.60   84
  8  \w   -134.00  43.00   0.50    0.76    --  -45.50   0.00 150.00  354
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0664490000
_diffrn_orient_matrix_UB_12      0.0756541000
_diffrn_orient_matrix_UB_13      0.1095340000
_diffrn_orient_matrix_UB_21      0.0607110000
_diffrn_orient_matrix_UB_22      -0.0258010000
_diffrn_orient_matrix_UB_23      -0.0598583000
_diffrn_orient_matrix_UB_31      0.0165012000
_diffrn_orient_matrix_UB_32      0.0446569000
_diffrn_orient_matrix_UB_33      -0.2207914000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0551
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            12794
_diffrn_reflns_point_group_measured_fraction_full 0.789
_diffrn_reflns_point_group_measured_fraction_max 0.754
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.831
_diffrn_reflns_theta_min         2.625
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.743
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72229
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       needle
_exptl_crystal_F_000             792
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethyl acetate'
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 1186 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.165
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         4066
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0702
_refine_ls_R_factor_gt           0.0645
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0620P)^2^+2.9322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1746
_refine_ls_wR_factor_ref         0.1803
_reflns_Friedel_coverage         0.548
_reflns_Friedel_fraction_full    0.578
_reflns_Friedel_fraction_max     0.534
_reflns_number_gt                3724
_reflns_number_total             4066
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03394_si_001.cif
_cod_data_source_block           exp_701
_cod_original_cell_volume        1988.02(10)
_cod_database_code               4514899
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 N13(H13), C32(H32), C4(H4), C36(H36), C2(H2), C6(H6), C35(H35), C34(H34),
 C33(H33), C5(H5), C3(H3)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C19(H19A,H19B,H19C), C26(H26A,H26B,H26C), C24(H24A,H24B,
 H24C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              24712
_shelx_hkl_checksum              85427
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.387
_oxdiff_exptl_absorpt_empirical_full_min 0.646