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_4135138
_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_absolute_configuration rmad
_chemical_formula_moiety         'C18 H20 N2 O'
_chemical_formula_sum            'C18 H20 N2 O'
_chemical_formula_weight         280.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difamp
_audit_creation_date             2020-03-12
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.0002(16)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.93221(11)
_cell_length_b                   7.41652(12)
_cell_length_c                   13.7616(3)
_cell_measurement_reflns_used    8868
_cell_measurement_temperature    139.9(4)
_cell_measurement_theta_max      75.8140
_cell_measurement_theta_min      5.9240
_cell_volume                     707.09(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.74a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.74a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.74a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.9(4)
_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   -115.00 -81.00   1.00    2.00    --  -40.66 -33.00 -89.00   34
  2  \w    -69.00 -15.00   1.00    2.00    --  -40.66 -33.00 -89.00   54
  3  \w     24.00  54.00   1.00    2.00    --   40.66  33.00  68.00   30
  4  \w    -34.00  34.00   1.00    2.00    --   40.66 -33.00 -89.00   68
  5  \w     78.00 103.00   1.00    8.00    --  112.00 -33.00 -89.00   25
  6  \w    115.00 140.00   1.00    8.00    --  112.00  33.00  68.00   25
  7  \w    -63.00  35.00   1.00    2.00    --  -40.66  33.00  68.00   98
  8  \w     60.00  91.00   1.00    2.00    --   40.66  33.00  68.00   31
  9  \w     27.00  92.00   1.00    2.00    --   40.66-125.00 -30.00   65
 10  \w     69.00  96.00   1.00    2.00    --   40.66  57.00 120.00   27
 11  \w     14.00  62.00   1.00    2.00    --   40.66  57.00 120.00   48
 12  \w      6.00  82.00   1.00    2.00    --   40.66 -99.00 120.00   76
 13  \w      7.00  32.00   1.00    2.00    --   42.00  84.00 168.89   25
 14  \w      7.00  32.00   1.00    2.00    --   42.00  84.00  61.12   25
 15  \w     12.00  37.00   1.00    2.00    --   46.00  82.00 -89.44   25
 16  \w     16.00  41.00   1.00    2.00    --   50.00  82.00  13.52   25
 17  \w     16.00  41.00   1.00    2.00    --   50.00  82.00 118.44   25
 18  \w     27.00  69.00   1.00    2.00    --   54.00  72.00 -71.49   42
 19  \w     98.00 132.00   1.00    2.00    --   58.00  71.00 -34.67   34
 20  \w     28.00  60.00   1.00    2.00    --   58.00  71.00 -34.67   32
 21  \w     31.00  56.00   1.00    2.00    --   58.00  74.00 134.04   25
 22  \w     80.00 122.00   1.00    2.00    --   62.00  73.00-122.16   42
 23  \w     36.00  75.00   1.00    2.00    --   62.00  73.00-122.16   39
 24  \w     36.00  84.00   1.00    2.00    --   66.00  74.00  36.56   48
 25  \w     98.00 125.00   1.00    2.00    --   66.00  74.00  36.56   27
 26  \w     34.00  69.00   1.00    2.00    --   66.00  73.00  -3.72   35
 27  \w     35.00  72.00   1.00    2.00    --   66.00  70.00-146.22   37
 28  \w     39.00  81.00   1.00    2.00    --   70.00  73.00 176.85   42
 29  \w     39.00  65.00   1.00    2.00    --   70.00  72.00 162.81   26
 30  \w     43.00  91.00   1.00    2.00    --   74.00  74.00  98.33   48
 31  \w     51.00  76.00   1.00    8.00    --   78.00  56.00  77.18   25
 32  \w     48.00  81.00   1.00    8.00    --   78.00  70.00  -7.85   33
 33  \w     94.00 152.00   1.00    8.00    --   78.00  70.00  -7.85   58
 34  \w     48.00  91.00   1.00    8.00    --   78.00  71.00 -59.02   43
 35  \w     78.00 104.00   1.00    8.00    --  106.00  61.00 120.90   26
 36  \w     84.00 128.00   1.00    8.00    --  112.00  61.00-180.00   44
 37  \w    151.00 178.00   1.00    8.00    --  112.00  45.00  30.00   27
 38  \w     88.00 133.00   1.00    8.00    --  112.00  45.00  30.00   45
 39  \w     88.00 115.00   1.00    8.00    --  112.00  45.00-180.00   27
 40  \w     84.00 169.00   1.00    8.00    --  112.00  61.00 -60.00   85
 41  \w    116.00 174.00   1.00    8.00    --  112.00 111.00-120.00   58
 42  \w     84.00 125.00   1.00    8.00    --  112.00  61.00 150.00   41
 43  \w    125.00 178.00   1.00    8.00    --  112.00  45.00 120.00   53
 44  \w     66.00 109.00   1.00    8.00    --  112.00-111.00 -90.00   43
 45  \w     94.00 133.00   1.00    8.00    --  112.00  45.00-120.00   39
 46  \w     42.00 140.00   1.00    8.00    --  112.00 -61.00-120.00   98
 47  \w    136.00 171.00   1.00    8.00    --  112.00  69.00  75.68   35
 48  \w     38.00  65.00   1.00    8.00    --  112.00-111.00 -90.00   27
 49  \w     31.00  67.00   1.00    8.00    --  112.00 -94.00  90.00   36
 50  \w     81.00 128.00   1.00    8.00    --  112.00  69.00  75.68   47
 51  \w     40.00 104.00   1.00    8.00    --  112.00-111.00-150.00   64
 52  \w     83.00 158.00   1.00    8.00    --  112.00  61.00 -90.00   75
 53  \w     83.00 172.00   1.00    8.00    --  112.00  61.00  60.00   89
 54  \w     87.00 178.00   1.00    8.00    --  112.00  61.00 -30.00   91
 55  \w    126.00 176.00   1.00    8.00    --  112.00  61.00   0.00   50
 56  \w     86.00 121.00   1.00    8.00    --  112.00  45.00 120.00   35
 57  \w     80.00 107.00   1.00    8.00    --  112.00 -94.00 -30.00   27
 58  \w     86.00 113.00   1.00    8.00    --  112.00  45.00 150.00   27
 59  \w    143.00 170.00   1.00    8.00    --  112.00  45.00 150.00   27
 60  \w    106.00 178.00   1.00    8.00    --  112.00 111.00-180.00   72
 61  \w     32.00  57.00   1.00    8.00    --  112.00 -94.00 -30.00   25
 62  \w     38.00 109.00   1.00    8.00    --  112.00-111.00  60.00   71
 63  \w     83.00 109.00   1.00    8.00    --  112.00  61.00   0.00   26
 64  \w     84.00 171.00   1.00    8.00    --  112.00  61.00-120.00   87
 65  \w     70.00 105.00   1.00    8.00    --  112.00-111.00-180.00   35
 66  \w     83.00 131.00   1.00    8.00    --  112.00  61.00  30.00   48
 67  \w     39.00  67.00   1.00    8.00    --  112.00 -77.00-150.00   28
 68  \w    130.00 161.00   1.00    8.00    --  112.00  61.00-180.00   31
 69  \w     38.00  68.00   1.00    8.00    --  112.00-111.00-180.00   30
 70  \w     83.00 148.00   1.00    8.00    --  112.00  61.00-150.00   65
 71  \w     96.00 123.00   1.00    8.00    --  112.00 -77.00-150.00   27
 72  \w     70.00 105.00   1.00    8.00    --  112.00 -94.00  90.00   35
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0854324000
_diffrn_orient_matrix_UB_12      0.1688419000
_diffrn_orient_matrix_UB_13      -0.0473721000
_diffrn_orient_matrix_UB_21      -0.1945621000
_diffrn_orient_matrix_UB_22      0.0979611000
_diffrn_orient_matrix_UB_23      0.0086223000
_diffrn_orient_matrix_UB_31      0.0653360000
_diffrn_orient_matrix_UB_32      0.0707562000
_diffrn_orient_matrix_UB_33      0.1012270000
_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  0.0270
_diffrn_reflns_av_unetI/netI     0.0162
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12955
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.135
_diffrn_reflns_theta_min         3.213
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.645
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.258
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.74a (Rigaku Oxford Diffraction, 2020)
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 yellow'
_exptl_crystal_density_diffrn    1.317
_exptl_crystal_description       irregular
_exptl_crystal_F_000             300
_exptl_crystal_size_max          0.576
_exptl_crystal_size_mid          0.372
_exptl_crystal_size_min          0.229
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     193
_refine_ls_number_reflns         2935
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0308
_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^)+(0.0524P)^2^+0.1115P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0840
_refine_ls_wR_factor_ref         0.0847
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                2881
_reflns_number_total             2935
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_002.cif
_cod_data_source_block           randres-arborisidineenantio
_cod_database_code               4135138
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H20 N2 O1'
_shelx_estimated_absorpt_t_max   0.866
_shelx_estimated_absorpt_t_min   0.708
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.1(3)
 -0.1(3)
2. 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
3.a Ternary CH refined with riding coordinates:
 C12(H12), C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C16(H16A,H16B), C17(H17A,H17B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              13854
_shelx_hkl_checksum              45682
_olex2_date_sample_data_collection 2020-03-11
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.427
_oxdiff_exptl_absorpt_empirical_full_min 0.510