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_4135127
_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_sum            'C27 H32 N2 O3'
_chemical_formula_weight         432.54
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                105.663(6)
_cell_angle_beta                 98.138(9)
_cell_angle_gamma                105.425(10)
_cell_formula_units_Z            2
_cell_length_a                   9.1818(13)
_cell_length_b                   9.8124(7)
_cell_length_c                   14.8937(9)
_cell_measurement_reflns_used    2437
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.3340
_cell_measurement_theta_min      3.1610
_cell_volume                     1212.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Mercury 4.1.0 (CCDC, 2019)'
_computing_publication_material  'CIFTab (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.956
_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   -116.00  -9.00   1.00    9.06    --  -40.41 -77.00   0.00  107
  2  \w   -115.00 -25.00   1.00    9.06    --  -40.41 -38.00-120.00   90
  3  \w     25.00  90.00   1.00    9.06    --   40.41-125.00-120.00   65
  4  \w      2.00  30.00   1.00    9.06    --   40.41 -99.00-120.00   28
  5  \w      1.00  66.00   1.00    9.06    --   40.41 -99.00 120.00   65
  6  \w     88.00 115.00   1.00    9.06    --   40.41  38.00  30.00   27
  7  \w    101.00 172.00   1.00   36.24    --  107.03 125.00   0.00   71
  8  \w     93.00 169.00   1.00   36.24    --  107.03  30.00   0.00   76
  9  \w     88.00 178.00   1.00   36.24    --  107.03  45.00  60.00   90
 10  \w     79.00 118.00   1.00   36.24    --  107.03-125.00  60.00   39
 11  \w     34.00 131.00   1.00   36.24    --  107.03 -77.00  60.00   97
 12  \w     39.00 118.00   1.00   36.24    --  107.03-125.00-120.00   79
 13  \w     76.00 134.00   1.00   36.24    --  107.03 -30.00-180.00   58
 14  \w    102.00 129.00   1.00   36.24    --  107.03 125.00 -90.00   27
 15  \w     34.00  97.00   1.00   36.24    --  107.03 -94.00 -60.00   63
 16  \w     38.00 134.00   1.00   36.24    --  107.03 -30.00  30.00   96
 17  \w     59.00 134.00   1.00   36.24    --  107.03 -61.00 -90.00   75
;
_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  0.0330
_diffrn_reflns_av_unetI/netI     0.0519
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8111
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.831
_diffrn_reflns_theta_min         3.166
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.612
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.608
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.20a (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       irregular
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.238
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.041
_refine_ls_extinction_coef       0.0038(7)
_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   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         4705
_refine_ls_number_restraints     117
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0520
_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^)+(0.0790P)^2^+0.0302P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1384
_refine_ls_wR_factor_ref         0.1552
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3506
_reflns_number_total             4705
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_004.cif
_cod_data_source_block           rat27
_cod_database_code               4135127
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.848
_shelx_estimated_absorpt_t_max   0.987
_shelx_res_checksum              85659
_shelx_hkl_checksum              49286