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_4135140
_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         'C24 H32 N2 O6 Si'
_chemical_formula_sum            'C24 H32 N2 O6 Si'
_chemical_formula_weight         472.60
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.4594(4)
_cell_length_b                   17.1371(12)
_cell_length_c                   33.460(2)
_cell_measurement_reflns_used    1878
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      68.6400
_cell_measurement_theta_min      5.1430
_cell_volume                     4850.7(5)
_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    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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   -109.00 -21.00   1.00   10.00    --  -42.88 -57.00 150.00   88
  2  \w    -75.00  26.00   1.00   10.00    --  -42.88  77.00  60.00  101
  3  \w   -107.00 -80.00   1.00   10.00    --  -42.88 -99.00-150.00   27
  4  \w    -90.00 -64.00   1.00   10.00    --  -42.88 125.00   0.00   26
  5  \w    -71.00  30.00   1.00   10.00    --  -42.88  57.00 -60.00  101
  6  \w    101.00 178.00   1.00   40.00    --  105.68  77.00  60.00   77
  7  \w     29.00  70.00   1.00   40.00    --  105.68-107.00 -86.00   41
  8  \w     53.00 111.00   1.00   40.00    --  105.68 -77.00 -90.00   58
  9  \w     43.00 128.00   1.00   40.00    --  105.68 -45.00 -90.00   85
 10  \w     45.00 127.00   1.00   40.00    --  105.68 -45.00   0.00   82
 11  \w     65.00 100.00   1.00   40.00    --  105.68 -94.00-150.00   35
 12  \w     87.00 112.00   1.00   40.00    --  105.68-107.00 -86.00   25
 13  \w     42.00 128.00   1.00   40.00    --  105.68 -45.00  90.00   86
 14  \w     81.00 118.00   1.00   40.00    --  105.68-125.00 120.00   37
 15  \w     71.00 109.00   1.00   40.00    --  105.68 -94.00   0.00   38
 16  \w     23.00 108.00   1.00   40.00    --  105.68 -94.00 120.00   85
 17  \w     18.00 163.00   1.00   40.00    --  105.68   0.00-120.00  145
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0050053000
_diffrn_orient_matrix_UB_12      0.0569842000
_diffrn_orient_matrix_UB_13      0.0356148000
_diffrn_orient_matrix_UB_21      0.0635839000
_diffrn_orient_matrix_UB_22      0.0656613000
_diffrn_orient_matrix_UB_23      -0.0270100000
_diffrn_orient_matrix_UB_31      -0.1705017000
_diffrn_orient_matrix_UB_32      0.0228939000
_diffrn_orient_matrix_UB_33      -0.0111022000
_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  0.1648
_diffrn_reflns_av_unetI/netI     0.0839
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            33184
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.667
_diffrn_reflns_theta_min         5.162
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.207
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.740
_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 light colourless'
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       needle
_exptl_crystal_F_000             2016
_exptl_crystal_size_max          0.641
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.383
_refine_diff_density_min         -0.329
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         4858
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1285
_refine_ls_R_factor_gt           0.0650
_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^)+(0.0795P)^2^+1.3798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1952
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2716
_reflns_number_total             4858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_009.cif
_cod_data_source_block           ra-tmsotfp2
_cod_original_cell_volume        4850.6(5)
_cod_database_code               4135140
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C24 H32 N2 O6 Si1 '
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.512
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C19(H19A,H19B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              41405
_shelx_hkl_checksum              49283
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.848
_oxdiff_exptl_absorpt_empirical_full_min 0.657