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_4135135
_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         'C20 H25 I N2 O3'
_chemical_formula_sum            'C20 H25 I N2 O3'
_chemical_formula_weight         468.32
_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                102.988(3)
_cell_angle_beta                 97.945(3)
_cell_angle_gamma                96.625(3)
_cell_formula_units_Z            4
_cell_length_a                   11.5067(4)
_cell_length_b                   11.7673(4)
_cell_length_c                   15.5305(5)
_cell_measurement_reflns_used    8495
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4940
_cell_measurement_theta_min      3.8520
_cell_volume                     2005.91(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Mercury 4.3.0 (CCDC, 2019)'
_computing_publication_material  'CIFTab (Sheldrick, 2016)'
_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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.970
_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    -68.00  30.00   1.00    1.00    --  -43.01  57.00 -60.00   98
  2  \w    -53.00  -6.00   1.00    1.00    --  -43.01 125.00  60.00   47
  3  \w   -108.00 -19.00   1.00    1.00    --  -43.01 -57.00 150.00   89
  4  \w    -21.00  72.00   1.00    1.00    --   43.01 -77.00  30.00   93
  5  \w     35.00 107.00   1.00    2.00    --  103.80 -94.00  30.00   72
  6  \w    131.00 177.00   1.00    2.00    --  103.80  77.00  60.00   46
  7  \w     44.00 129.00   1.00    2.00    --  103.80 -30.00 120.00   85
  8  \w     65.00 107.00   1.00    2.00    --  103.80-111.00 150.00   42
  9  \w    139.00 175.00   1.00    2.00    --  103.80 111.00  30.00   36
 10  \w     29.00 155.00   1.00    2.00    --  103.80 -15.00 -30.00  126
 11  \w    153.00 178.00   1.00    2.00    --  103.80 111.00   0.00   25
 12  \w     27.00  85.00   1.00    2.00    --  103.80 -94.00-180.00   58
 13  \w     59.00 106.00   1.00    2.00    --  103.80-111.00-120.00   47
 14  \w    119.00 175.00   1.00    2.00    --  103.80 111.00  90.00   56
 15  \w     84.00 174.00   1.00    2.00    --  103.80  45.00 150.00   90
 16  \w     59.00 131.00   1.00    2.00    --  103.80 -61.00   0.00   72
 17  \w     69.00 127.00   1.00    2.00    --  103.80-144.00  28.16   58
;
_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  0.0215
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14901
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.657
_diffrn_reflns_theta_min         3.900
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.717
_exptl_absorpt_correction_T_max  0.224
_exptl_absorpt_correction_T_min  0.049
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear intense yellow'
_exptl_crystal_density_diffrn    1.551
_exptl_crystal_description       prism
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.451
_exptl_crystal_size_mid          0.323
_exptl_crystal_size_min          0.258
_refine_diff_density_max         0.876
_refine_diff_density_min         -1.154
_refine_diff_density_rms         0.085
_refine_ls_extinction_coef       0.00071(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   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         7744
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0315
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0576P)^2^+0.5918P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0836
_refine_ls_wR_factor_ref         0.0846
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7418
_reflns_number_total             7744
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_012.cif
_cod_data_source_block           randres-6rat121-1-p2b
_cod_original_cell_volume        2005.90(12)
_cod_database_code               4135135
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.069
_shelx_estimated_absorpt_t_max   0.138
_shelx_res_checksum              8608
_shelx_hkl_checksum              62604