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_4135133
_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         'C15 H22 N2 O3'
_chemical_formula_sum            'C15 H22 N2 O3'
_chemical_formula_weight         278.34
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 94.605(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4960(10)
_cell_length_b                   6.8584(5)
_cell_length_c                   12.8051(8)
_cell_measurement_reflns_used    2206
_cell_measurement_temperature    140.01(10)
_cell_measurement_theta_max      70.9600
_cell_measurement_theta_min      5.3040
_cell_volume                     1444.04(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Mercury 4.1.3 (CCDC, 2019)'
_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      140.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_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   -115.00 -18.00   1.00   10.00    --  -43.26 -57.00 150.00   97
  2  \w    -41.00 -12.00   1.00   10.00    --  -43.26 125.00 -60.00   29
  3  \w    -62.00  31.00   1.00   10.00    --  -43.26  37.00 -60.00   93
  4  \w    -89.00  -5.00   1.00   10.00    --  -43.26 125.00   0.00   84
  5  \w    -84.00 -58.00   1.00   10.00    --  -43.26 125.00 -60.00   26
  6  \w     76.00 103.00   1.00   40.00    --  103.18 178.00 150.00   27
  7  \w    110.00 178.00   1.00   40.00    --  103.18 111.00 -60.00   68
  8  \w     72.00 170.00   1.00   40.00    --  103.18  77.00 -90.00   98
  9  \w     22.00  72.00   1.00   40.00    --  103.18 -15.00-180.00   50
 10  \w     35.00 103.00   1.00   40.00    --  103.18-111.00 150.00   68
 11  \w    105.00 152.00   1.00   40.00    --  103.18 -15.00-180.00   47
 12  \w     68.00 113.00   1.00   40.00    --  103.18-111.00  30.00   45
 13  \w     30.00  57.00   1.00   40.00    --  103.18-111.00-120.00   27
 14  \w     81.00 113.00   1.00   40.00    --  103.18-111.00-120.00   32
 15  \w     31.00 129.00   1.00   40.00    --  103.18 -45.00 -60.00   98
 16  \w     43.00 134.00   1.00   40.00    --  103.18 -77.00-150.00   91
 17  \w    100.00 155.00   1.00   40.00    --  103.18  61.00   0.00   55
 18  \w     59.00 140.00   1.00   40.00    --  103.18 178.00-180.00   81
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_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  0.0726
_diffrn_reflns_av_unetI/netI     0.0604
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9691
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.531
_diffrn_reflns_theta_min         5.381
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.726
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.390
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.280
_exptl_crystal_description       irregular
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.368
_exptl_crystal_size_mid          0.293
_exptl_crystal_size_min          0.142
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         2806
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0889
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0904P)^2^+0.3147P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1572
_refine_ls_wR_factor_ref         0.1798
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2003
_reflns_number_total             2806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_016.cif
_cod_data_source_block           randres-4RAT3
_cod_original_cell_volume        1444.05(16)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4135133
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.776
_shelx_estimated_absorpt_t_max   0.904
_shelx_res_checksum              8558
_shelx_hkl_checksum              49093