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_4135136
_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      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                84.564(3)
_cell_angle_beta                 87.962(3)
_cell_angle_gamma                74.981(3)
_cell_formula_units_Z            2
_cell_length_a                   8.3248(2)
_cell_length_b                   10.4978(3)
_cell_length_c                   14.7652(5)
_cell_measurement_reflns_used    6168
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.4950
_cell_measurement_theta_min      4.3590
_cell_volume                     1240.60(7)
_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    'Mercury 4.0.0 (CCDC, 2018)'
_computing_publication_material  'CIFTab (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -61.00  35.00   1.00    4.41    --  -40.91  77.00-180.00   96
  2  \w   -112.00 -13.00   1.00    4.41    --  -40.91 -57.00  60.00   99
  3  \w     24.00  95.00   1.00    4.41    --   40.91  38.00 -60.00   71
  4  \w      3.00  76.00   1.00    4.41    --   40.91 -99.00 -60.00   73
  5  \w      0.00  59.00   1.00    4.41    --   40.91 -38.00 -90.00   59
  6  \w     33.00  73.00   1.00    4.41    --   40.91 -77.00 -30.00   40
  7  \w     79.00 113.00   1.00   17.65    --  112.00-111.00-120.00   34
  8  \w    111.00 139.00   1.00   17.65    --  112.00 -61.00-150.00   28
  9  \w    108.00 175.00   1.00   17.65    --  112.00 111.00 150.00   67
 10  \w     50.00 124.00   1.00   17.65    --  112.00 -30.00 -30.00   74
 11  \w    100.00 177.00   1.00   17.65    --  112.00  61.00 -60.00   77
 12  \w    139.00 175.00   1.00   17.65    --  112.00 111.00 -30.00   36
 13  \w     43.00  69.00   1.00   17.65    --  112.00 -77.00 150.00   26
 14  \w     55.00 110.00   1.00   17.65    --  112.00-111.00 150.00   55
 15  \w     54.00 109.00   1.00   17.65    --  112.00-111.00  30.00   55
 16  \w     43.00  73.00   1.00   17.65    --  112.00 -61.00-150.00   30
 17  \w     77.00 105.00   1.00   17.65    --  112.00 -94.00 150.00   28
 18  \w     29.00  55.00   1.00   17.65    --  112.00 -94.00 150.00   26
 19  \w     83.00 111.00   1.00   17.65    --  112.00-111.00  90.00   28
 20  \w     87.00 121.00   1.00   17.65    --  112.00  45.00 120.00   34
 21  \w    143.00 175.00   1.00   17.65    --  112.00  45.00 120.00   32
 22  \w     51.00 113.00   1.00   17.65    --  112.00-111.00 -60.00   62
 23  \w     96.00 125.00   1.00   17.65    --  112.00  15.00  90.00   29
 24  \w    131.00 158.00   1.00   17.65    --  112.00  15.00  90.00   27
 25  \w     30.00 103.00   1.00   17.65    --  112.00 -94.00 -60.00   73
 26  \w    108.00 142.00   1.00   17.65    --  112.00 178.00 150.00   34
 27  \w    100.00 172.00   1.00   17.65    --  112.00  45.00   0.00   72
 28  \w     99.00 126.00   1.00   17.65    --  112.00 -77.00 150.00   27
 29  \w     47.00  87.00   1.00   17.65    --  112.00-111.00 120.00   40
 30  \w     42.00  88.00   1.00   17.65    --  112.00-111.00-150.00   46
 31  \w     66.00 161.00   1.00   17.65    --  112.00  15.00 -60.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_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  0.0208
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11684
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.021
_diffrn_reflns_theta_min         3.007
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.743
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_description       plate
_exptl_crystal_F_000             476
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.167
_refine_diff_density_rms         0.034
_refine_ls_extinction_coef       0.0013(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   1.038
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     426
_refine_ls_number_reflns         5138
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0494P)^2^+0.1723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0898
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4453
_reflns_number_total             5138
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_006.cif
_cod_data_source_block           randres-H2BocP3
_cod_database_code               4135136
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.884
_shelx_estimated_absorpt_t_max   0.923
_shelx_res_checksum              28138
_shelx_hkl_checksum              5110