Asymmetric Total Synthesis of (-)-Arborisidine and (-)-19-epi-Arborisidine Enabled by a Catalytic Enantioselective Pictet-Spengler Reaction.
Andres, Rémi; Wang, Qian; Zhu, Jieping; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c05804

data_4135137
_publ_section_title
;
 Asymmetric Total Synthesis of (-)-Arborisidine and
 (-)-19-epi-Arborisidine Enabled by a Catalytic Enantioselective
 Pictet-Spengler Reaction.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c05804
_journal_year                    2020
_chemical_formula_moiety         'C25 H34 N2 O5'
_chemical_formula_sum            'C25 H34 N2 O5'
_chemical_formula_weight         442.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.53(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.313(11)
_cell_length_b                   16.775(14)
_cell_length_c                   11.290(3)
_cell_measurement_reflns_used    354
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.8920
_cell_measurement_theta_min      3.4440
_cell_volume                     2391(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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   -110.00 -74.00   1.00   30.00    --  -41.16 -57.00 -30.00   36
  2  \w    -21.00  66.00   1.00   30.00    --   41.16 -38.00  90.00   87
  3  \w     44.00  92.00   1.00   30.00    --   41.16-125.00 -60.00   48
  4  \w     25.00  99.00   1.00   30.00    --   41.16  57.00-120.00   74
  5  \w     35.00 115.00   1.00  120.00    --  107.03-125.00   0.00   80
  6  \w     87.00 114.00   1.00  120.00    --  107.03  61.00 -60.00   27
  7  \w     57.00 123.00   1.00  120.00    --  107.03 -30.00  60.00   66
  8  \w     83.00 110.00   1.00  120.00    --  107.03 -94.00 150.00   27
  9  \w     79.00 176.00   1.00  120.00    --  107.03  30.00  60.00   97
 10  \w     94.00 158.00   1.00  120.00    --  107.03 125.00-116.00   64
 11  \w     36.00 108.00   1.00  120.00    --  107.03 -94.00  60.00   72
 12  \w    113.00 170.00   1.00  120.00    --  107.03 125.00 120.00   57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0162777000
_diffrn_orient_matrix_UB_12      0.0878772000
_diffrn_orient_matrix_UB_13      0.0289209000
_diffrn_orient_matrix_UB_21      0.1087902000
_diffrn_orient_matrix_UB_22      0.0210536000
_diffrn_orient_matrix_UB_23      -0.0122345000
_diffrn_orient_matrix_UB_31      -0.0524000000
_diffrn_orient_matrix_UB_32      0.0163278000
_diffrn_orient_matrix_UB_33      -0.1405935000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.3394
_diffrn_reflns_av_unetI/netI     0.3416
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5867
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        50.436
_diffrn_reflns_theta_max         50.436
_diffrn_reflns_theta_min         3.501
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.692
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45266
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_description       needle
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.399
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.112
_refine_ls_extinction_coef       0.0004(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.938
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         2462
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      0.891
_refine_ls_R_factor_all          0.2593
_refine_ls_R_factor_gt           0.1427
_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^)+(0.1035P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2924
_refine_ls_wR_factor_ref         0.3554
_reflns_Friedel_coverage         0.000
_reflns_number_gt                796
_reflns_number_total             2462
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_005.cif
_cod_data_source_block           randres-h2bocp2
_cod_database_code               4135137
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H34 N2 O5'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.814
_reflns_odcompleteness_completeness 97.19
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C10(H10A,H10B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C5(H5), C7(H7), C6(H6)
3.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C12(H12A,H12B,H12C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C)
;
_shelx_res_checksum              95237
_shelx_hkl_checksum              10047
_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 2.082
_oxdiff_exptl_absorpt_empirical_full_min 0.580