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_4135139
_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         'C15 H18 N2 O2'
_chemical_formula_sum            'C15 H18 N2 O2'
_chemical_formula_weight         258.31
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.445(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.4744(3)
_cell_length_b                   9.0004(3)
_cell_length_c                   9.4211(3)
_cell_measurement_reflns_used    4601
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.2810
_cell_measurement_theta_min      4.6680
_cell_volume                     632.64(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (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 0.987
_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      6.00  32.00   1.00    3.00    --   42.00  87.00 151.76   26
  2  \w    -54.00 -19.00   1.00    3.00    --  -43.01 -37.00-150.00   35
  3  \w    -56.00 -16.00   1.00    3.00    --  -43.01 -57.00 120.00   40
  4  \w    -54.00 -17.00   1.00    3.00    --  -43.01 -57.00  30.00   37
  5  \w   -107.00 -77.00   1.00    3.00    --  -43.01 -37.00-150.00   30
  6  \w    -98.00 -73.00   1.00    3.00    --  -43.01 -57.00 120.00   25
  7  \w   -113.00 -79.00   1.00    3.00    --  -43.01 -99.00   0.00   34
  8  \w   -114.00 -75.00   1.00    3.00    --  -43.01 -57.00  30.00   39
  9  \w     23.00  68.00   1.00    3.00    --   43.01-125.00-150.00   45
 10  \w     11.00  82.00   1.00    3.00    --   43.01 -99.00  30.00   71
 11  \w     70.00  96.00   1.00    3.00    --   43.01-125.00-150.00   26
 12  \w     13.00  39.00   1.00    3.00    --   46.00  80.00 -34.16   26
 13  \w     15.00  40.00   1.00    3.00    --   46.00  82.00-126.93   25
 14  \w     17.00  42.00   1.00    3.00    --   50.00  80.00  24.14   25
 15  \w     16.00  41.00   1.00    3.00    --   50.00  82.00  71.83   25
 16  \w     27.00  64.00   1.00    3.00    --   58.00  76.00 -14.15   37
 17  \w     98.00 132.00   1.00    3.00    --   58.00  77.00 144.94   34
 18  \w     25.00  59.00   1.00    3.00    --   58.00  77.00 144.94   34
 19  \w     32.00  58.00   1.00    3.00    --   62.00  64.00  74.15   26
 20  \w     30.00  58.00   1.00    3.00    --   62.00  75.00-139.60   28
 21  \w     33.00  59.00   1.00    3.00    --   66.00  77.00  76.65   26
 22  \w     90.00 138.00   1.00    3.00    --   66.00  77.00  76.65   48
 23  \w     40.00  66.00   1.00    3.00    --   70.00  73.00  79.61   26
 24  \w     39.00  66.00   1.00    3.00    --   70.00  77.00-112.45   27
 25  \w     42.00  74.00   1.00    3.00    --   70.00  75.00 -85.04   32
 26  \w     46.00  72.00   1.00   12.00    --   78.00  76.00 132.29   26
 27  \w    122.00 154.00   1.00   12.00    --   78.00  77.00 -14.93   32
 28  \w     45.00  77.00   1.00   12.00    --   78.00  77.00 -14.93   32
 29  \w     48.00  74.00   1.00   12.00    --   78.00  66.00-144.37   26
 30  \w     54.00  81.00   1.00   12.00    --   86.00  75.00 146.09   27
 31  \w     58.00  84.00   1.00   12.00    --   86.00  74.00 -46.56   26
 32  \w    120.00 158.00   1.00   12.00    --   86.00  70.00  86.25   38
 33  \w     58.00  84.00   1.00   12.00    --   86.00  70.00  86.25   26
 34  \w     60.00  86.00   1.00   12.00    --   90.00  64.00 113.94   26
 35  \w    103.00 143.00   1.00   12.00    --   94.00  68.00-109.49   40
 36  \w     68.00  96.00   1.00   12.00    --   94.00  68.00-109.49   28
 37  \w    104.00 132.00   1.00   12.00    --  105.68 -45.00 -30.00   28
 38  \w     46.00  85.00   1.00   12.00    --  105.68 -45.00 -30.00   39
 39  \w     80.00 128.00   1.00   12.00    --  105.68  61.00  60.00   48
 40  \w     76.00 158.00   1.00   12.00    --  105.68  77.00 -60.00   82
 41  \w     76.00 151.00   1.00   12.00    --  105.68  77.00 -90.00   75
 42  \w     74.00 135.00   1.00   12.00    --  105.68  76.00-171.00   61
 43  \w     78.00 168.00   1.00   12.00    --  105.68  77.00 150.00   90
 44  \w    103.00 129.00   1.00   12.00    --  105.68  77.00   0.00   26
 45  \w    124.00 175.00   1.00   12.00    --  105.68 125.00 -90.00   51
 46  \w     74.00 100.00   1.00   12.00    --  105.68  77.00   0.00   26
 47  \w     24.00 102.00   1.00   12.00    --  105.68 -94.00 -30.00   78
 48  \w     73.00 178.00   1.00   12.00    --  105.68  77.00 -30.00  105
 49  \w     49.00 108.00   1.00   12.00    --  105.68 -94.00  60.00   59
 50  \w    130.00 156.00   1.00   12.00    --  105.68 125.00-120.00   26
 51  \w     51.00 117.00   1.00   12.00    --  105.68-125.00 -90.00   66
 52  \w     77.00 104.00   1.00   12.00    --  105.68  61.00 -90.00   27
 53  \w    115.00 161.00   1.00   12.00    --  105.68  77.00-150.00   46
 54  \w     74.00 139.00   1.00   12.00    --  105.68  77.00  90.00   65
 55  \w     76.00 102.00   1.00   12.00    --  105.68  77.00-150.00   26
 56  \w    122.00 153.00   1.00   12.00    --  105.68  61.00  30.00   31
 57  \w     88.00 114.00   1.00   12.00    --  105.68  61.00  30.00   26
 58  \w     79.00 160.00   1.00   12.00    --  105.68  77.00 120.00   81
 59  \w     96.00 169.00   1.00   12.00    --  105.68 125.00  30.00   73
;
_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      -0.1717748000
_diffrn_orient_matrix_UB_12      0.0528174000
_diffrn_orient_matrix_UB_13      -0.0835243000
_diffrn_orient_matrix_UB_21      -0.0288198000
_diffrn_orient_matrix_UB_22      0.1176462000
_diffrn_orient_matrix_UB_23      0.1151965000
_diffrn_orient_matrix_UB_31      0.1109094000
_diffrn_orient_matrix_UB_32      0.1124866000
_diffrn_orient_matrix_UB_33      -0.0812412000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            9756
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.716
_diffrn_reflns_theta_min         4.702
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.732
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.587
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.20a (Rigaku Oxford Diffraction, 2018).
 Numerical absorption correction based on Gaussian integration over
 a multifaceted crystal model.
 Empirical absorption correction using spherical harmonics
 as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       prism
_exptl_crystal_F_000             276
_exptl_crystal_size_max          0.314
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.083
_refine_diff_density_max         0.195
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1002 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         2487
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0323
_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^)+(0.0423P)^2^+0.0897P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0803
_refine_ls_wR_factor_ref         0.0828
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                2326
_reflns_number_total             2487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_015.cif
_cod_data_source_block           ra-2rat117
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               4135139
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C15 H16 N2 O1'
_reflns_odcompleteness_completeness 100.00
_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:
 C1(H1A), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_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 2.457
_oxdiff_exptl_absorpt_empirical_full_min 0.557