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_4135130
_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         'C27 H32 N2 O4, C H4 O'
_chemical_formula_sum            'C28 H36 N2 O5'
_chemical_formula_weight         480.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 98.262(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1569(2)
_cell_length_b                   30.0858(7)
_cell_length_c                   9.35117(19)
_cell_measurement_reflns_used    8935
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.5180
_cell_measurement_theta_min      4.9890
_cell_volume                     2549.44(10)
_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 4.1.0 (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      140.00(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 0.993
_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    -62.00 -13.00   1.00    6.00    --  -40.91  57.00  60.00   49
  2  \w   -108.00 -14.00   1.00    6.00    --  -40.91 -57.00 -90.00   94
  3  \w   -121.00  -2.00   1.00    6.00    --  -40.91 -19.00 120.00  119
  4  \w    -59.00 -33.00   1.00    6.00    --  -40.91 125.00 120.00   26
  5  \w     -3.00  32.00   1.00    6.00    --  -40.91  57.00  60.00   35
  6  \w     48.00  95.00   1.00    6.00    --   40.91-125.00-120.00   47
  7  \w     24.00  70.00   1.00    6.00    --   40.91-125.00 120.00   46
  8  \w     62.00 104.00   1.00   24.00    --  112.00 178.00-120.00   42
  9  \w     64.00  91.00   1.00   24.00    --  112.00-111.00 -60.00   27
 10  \w     88.00 115.00   1.00   24.00    --  112.00 -15.00  90.00   27
 11  \w     31.00 109.00   1.00   24.00    --  112.00 -94.00 150.00   78
 12  \w    110.00 141.00   1.00   24.00    --  112.00 178.00 150.00   31
 13  \w     72.00 123.00   1.00   24.00    --  112.00 -61.00 -30.00   51
 14  \w    121.00 146.00   1.00   24.00    --  112.00 178.00-120.00   25
 15  \w     81.00 108.00   1.00   24.00    --  112.00 -94.00  60.00   27
 16  \w    111.00 172.00   1.00   24.00    --  112.00 111.00-150.00   61
 17  \w     32.00  58.00   1.00   24.00    --  112.00 -94.00  60.00   26
 18  \w     86.00 140.00   1.00   24.00    --  112.00 -30.00-180.00   54
 19  \w     36.00  68.00   1.00   24.00    --  112.00 -30.00-180.00   32
 20  \w     57.00 113.00   1.00   24.00    --  112.00-111.00-150.00   56
 21  \w     85.00 112.00   1.00   24.00    --  112.00-111.00 -90.00   27
 22  \w     93.00 167.00   1.00   24.00    --  112.00  30.00  30.00   74
 23  \w     66.00  93.00   1.00   24.00    --  112.00 178.00-150.00   27
 24  \w     61.00  97.00   1.00   24.00    --  112.00 178.00 150.00   36
 25  \w     39.00  89.00   1.00   24.00    --  112.00 -94.00 -30.00   50
 26  \w     78.00 113.00   1.00   24.00    --  112.00-111.00 -30.00   35
 27  \w     40.00 120.00   1.00   24.00    --  112.00 -61.00-180.00   80
 28  \w     98.00 175.00   1.00   24.00    --  112.00  61.00 -30.00   77
 29  \w     94.00 176.00   1.00   24.00    --  112.00  77.00-120.00   82
 30  \w     42.00  69.00   1.00   24.00    --  112.00 -94.00-180.00   27
 31  \w     34.00  78.00   1.00   24.00    --  112.00 -15.00  90.00   44
 32  \w    105.00 138.00   1.00   24.00    --  112.00 178.00-150.00   33
 33  \w     67.00 126.00   1.00   24.00    --  112.00 -45.00 -90.00   59
 34  \w    110.00 174.00   1.00   24.00    --  112.00 111.00  60.00   64
 35  \w     51.00 113.00   1.00   24.00    --  112.00-111.00  30.00   62
;
_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  0.0352
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            25991
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.203
_diffrn_reflns_theta_min         2.938
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.691
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.845
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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 pale colourless'
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       plate
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.258
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.266
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.00030(12)
_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   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     459
_refine_ls_number_reflns         5312
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0408
_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^)+(0.0419P)^2^+0.9412P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1017
_refine_ls_wR_factor_ref         0.1065
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4574
_reflns_number_total             5312
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_007.cif
_cod_data_source_block           rati2nisp1
_cod_original_cell_volume        2549.45(10)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4135130
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.769
_shelx_estimated_absorpt_t_max   0.941
_shelx_res_checksum              4507
_shelx_hkl_checksum              88909