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_4135134
_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         'C22 H28 N2 O3'
_chemical_formula_sum            'C22 H28 N2 O3'
_chemical_formula_weight         368.46
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                83.102(11)
_cell_angle_beta                 89.166(8)
_cell_angle_gamma                76.743(11)
_cell_formula_units_Z            2
_cell_length_a                   7.4352(7)
_cell_length_b                   11.778(2)
_cell_length_c                   11.8822(12)
_cell_measurement_reflns_used    1653
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.1180
_cell_measurement_theta_min      5.0170
_cell_volume                     1005.4(2)
_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 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 0.969
_diffrn_measured_fraction_theta_max 0.929
_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   -122.00 -85.00   1.00    2.50    --  -42.76 -99.00-120.00   37
  2  \w    -81.00  32.00   1.00    2.50    --  -42.76  19.00-180.00  113
  3  \w    -60.00  30.00   1.00    2.50    --  -42.76  57.00-120.00   90
  4  \w      4.00  80.00   1.00    2.50    --   42.76 -99.00  30.00   76
  5  \w     30.00  57.00   1.00    2.50    --   42.76-125.00 -30.00   27
  6  \w     37.00 103.00   1.00   10.00    --  105.68 -94.00 120.00   66
  7  \w     74.00 127.00   1.00   10.00    --  105.68 -30.00 -30.00   53
  8  \w     34.00  74.00   1.00   10.00    --  105.68 -45.00 120.00   40
  9  \w    126.00 178.00   1.00   10.00    --  105.68  30.00  30.00   52
 10  \w     40.00 135.00   1.00   10.00    --  105.68 -61.00-120.00   95
 11  \w     25.00  82.00   1.00   10.00    --  105.68 -94.00  60.00   57
 12  \w     27.00 109.00   1.00   10.00    --  105.68 -94.00-150.00   82
 13  \w     32.00  59.00   1.00   10.00    --  105.68 -30.00 -30.00   27
 14  \w    138.00 178.00   1.00   10.00    --  105.68  61.00 -90.00   40
 15  \w     24.00 155.00   1.00   10.00    --  105.68 -15.00-150.00  131
 16  \w     92.00 128.00   1.00   10.00    --  105.68 -45.00 120.00   36
 17  \w     84.00 113.00   1.00   10.00    --  105.68-125.00  30.00   29
;
_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      0.0339176000
_diffrn_orient_matrix_UB_12      -0.0602079000
_diffrn_orient_matrix_UB_13      -0.1090087000
_diffrn_orient_matrix_UB_21      -0.0140484000
_diffrn_orient_matrix_UB_22      -0.1175464000
_diffrn_orient_matrix_UB_23      0.0678390000
_diffrn_orient_matrix_UB_31      -0.2097013000
_diffrn_orient_matrix_UB_32      0.0296376000
_diffrn_orient_matrix_UB_33      -0.0239571000
_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  0.0378
_diffrn_reflns_av_unetI/netI     0.0544
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            5963
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.629
_diffrn_reflns_theta_min         3.747
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.647
_exptl_absorpt_correction_T_max  0.977
_exptl_absorpt_correction_T_min  0.769
_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    1.217
_exptl_crystal_description       plate
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.899
_exptl_crystal_size_mid          0.282
_exptl_crystal_size_min          0.051
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     249
_refine_ls_number_reflns         3778
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0981
_refine_ls_R_factor_gt           0.0785
_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^)+(0.1449P)^2^+0.4540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2172
_refine_ls_wR_factor_ref         0.2395
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2792
_reflns_number_total             3778
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_014.cif
_cod_data_source_block           randres-2rat113dp
_cod_database_code               4135134
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H28 N2 O3'
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.594
_reflns_odcompleteness_completeness 96.99
_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 Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C16(H16A,H16B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              46093
_shelx_hkl_checksum              17151
_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 2.161
_oxdiff_exptl_absorpt_empirical_full_min 0.563