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_4135129
_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 O'
_chemical_formula_sum            'C15 H18 N2 O'
_chemical_formula_weight         242.31
_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   difmap
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.10.11 svn.r3662 for OlexSys, GUI svn.r5962)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.116(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.28461(18)
_cell_length_b                   8.30644(17)
_cell_length_c                   11.2310(3)
_cell_measurement_reflns_used    6915
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4800
_cell_measurement_theta_min      4.0640
_cell_volume                     649.48(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (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    'ShelXT 2018/2 (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     -4.00  21.00   1.00    1.00    --   34.00  91.00-117.25   25
  2  \w   -116.00 -80.00   1.00    1.00    --  -43.01 -37.00  30.00   36
  3  \w    -53.00 -19.00   1.00    1.00    --  -43.01 -37.00 150.00   34
  4  \w    -75.00 -21.00   1.00    1.00    --  -43.01 -37.00  30.00   54
  5  \w    -86.00  -7.00   1.00    1.00    --  -43.01 125.00   0.00   79
  6  \w      7.00  76.00   1.00    1.00    --   43.01 -99.00-120.00   69
  7  \w     12.00  38.00   1.00    1.00    --   46.00  81.00  63.67   26
  8  \w     13.00  41.00   1.00    1.00    --   46.00  80.00 -82.56   28
  9  \w     13.00  38.00   1.00    1.00    --   46.00  79.00 151.04   25
 10  \w     16.00  41.00   1.00    1.00    --   50.00  81.00 -24.83   25
 11  \w     16.00  42.00   1.00    1.00    --   50.00  81.00  32.67   26
 12  \w     23.00  54.00   1.00    1.00    --   54.00  71.00-176.99   31
 13  \w     27.00  65.00   1.00    1.00    --   58.00  74.00  68.08   38
 14  \w     29.00  74.00   1.00    1.00    --   58.00  73.00-104.27   45
 15  \w     81.00 133.00   1.00    1.00    --   58.00  73.00-104.27   52
 16  \w     90.00 115.00   1.00    1.00    --   58.00  74.00  68.08   25
 17  \w     32.00  60.00   1.00    1.00    --   62.00  72.00-142.03   28
 18  \w     36.00  67.00   1.00    1.00    --   66.00  67.00 123.50   31
 19  \w     79.00 138.00   1.00    1.00    --   66.00  67.00 123.50   59
 20  \w     94.00 135.00   1.00    1.00    --   70.00  74.00 -33.07   41
 21  \w     38.00  68.00   1.00    1.00    --   70.00  74.00 -33.07   30
 22  \w     44.00  81.00   1.00    4.00    --   74.00  73.00 149.67   37
 23  \w    106.00 143.00   1.00    4.00    --   78.00  68.00 -72.56   37
 24  \w     48.00  74.00   1.00    4.00    --   78.00  68.00 -72.56   26
 25  \w     52.00  90.00   1.00    4.00    --   78.00  55.00-109.92   38
 26  \w     52.00  93.00   1.00    4.00    --   82.00  68.00  34.34   41
 27  \w     58.00  85.00   1.00    4.00    --   86.00  62.00 -52.06   27
 28  \w     59.00  86.00   1.00    4.00    --   90.00  70.00 -18.48   27
 29  \w     66.00  99.00   1.00    4.00    --   94.00  57.00 157.48   33
 30  \w    125.00 157.00   1.00    4.00    --   94.00  57.00 157.48   32
 31  \w    105.00 160.00   1.00    4.00    --  103.80 111.00-150.00   55
 32  \w    108.00 178.00   1.00    4.00    --  103.80  77.00  30.00   70
 33  \w     21.00  90.00   1.00    4.00    --  103.80 -94.00-180.00   69
 34  \w     81.00 176.00   1.00    4.00    --  103.80  45.00 -30.00   95
 35  \w    148.00 176.00   1.00    4.00    --  103.80 111.00  90.00   28
 36  \w     22.00 103.00   1.00    4.00    --  103.80 -94.00  30.00   81
 37  \w     77.00 168.00   1.00    4.00    --  103.80  61.00 -90.00   91
 38  \w     75.00 136.00   1.00    4.00    --  103.80  61.00  30.00   61
 39  \w     76.00 143.00   1.00    4.00    --  103.80  61.00  90.00   67
 40  \w     75.00 148.00   1.00    4.00    --  103.80  61.00-150.00   73
 41  \w     37.00 106.00   1.00    4.00    --  103.80-111.00 150.00   69
 42  \w     75.00 172.00   1.00    4.00    --  103.80  61.00 120.00   97
 43  \w     76.00 107.00   1.00    4.00    --  103.80-111.00 -30.00   31
 44  \w     75.00 118.00   1.00    4.00    --  103.80  61.00-120.00   43
 45  \w     28.00  71.00   1.00    4.00    --  103.80-111.00 -30.00   43
 46  \w    133.00 176.00   1.00    4.00    --  103.80  61.00-180.00   43
 47  \w     75.00 110.00   1.00    4.00    --  103.80  61.00-180.00   35
 48  \w     76.00 101.00   1.00    4.00    --  103.80  60.00-160.35   25
 49  \w     78.00 119.00   1.00    4.00    --  103.80  61.00   0.00   41
 50  \w    135.00 161.00   1.00    4.00    --  103.80  61.00   0.00   26
 51  \w     77.00 102.00   1.00    4.00    --  103.80  61.00  60.00   25
 52  \w     30.00  97.00   1.00    4.00    --  103.80 -94.00-120.00   67
;
_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      0.0071040000
_diffrn_orient_matrix_UB_12      -0.1479363000
_diffrn_orient_matrix_UB_13      0.0839145000
_diffrn_orient_matrix_UB_21      -0.1807660000
_diffrn_orient_matrix_UB_22      0.0604458000
_diffrn_orient_matrix_UB_23      0.0307567000
_diffrn_orient_matrix_UB_31      -0.1274865000
_diffrn_orient_matrix_UB_32      -0.0940563000
_diffrn_orient_matrix_UB_33      -0.1123241000
_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  0.0149
_diffrn_reflns_av_unetI/netI     0.0098
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9811
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.634
_diffrn_reflns_theta_min         4.119
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.619
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.196
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
 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    1.239
_exptl_crystal_description       plate
_exptl_crystal_F_000             260
_exptl_crystal_size_max          0.786
_exptl_crystal_size_mid          0.369
_exptl_crystal_size_min          0.115
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.118
_refine_diff_density_rms         0.025
_refine_ls_abs_structure_details
;
 Flack x determined using 1144 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.12(5)
_refine_ls_extinction_coef       0.0137(14)
_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   1.057
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         2532
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0239
_refine_ls_R_factor_gt           0.0239
_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^)+(0.0366P)^2^+0.0783P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0623
_refine_ls_wR_factor_ref         0.0624
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                2521
_reflns_number_total             2532
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_003.cif
_cod_data_source_block           randres-6rat89-15
_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               4135129
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C15 H18 N2 O'
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.642
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
;
_shelx_res_checksum              74326
_shelx_hkl_checksum              48248
_olex2_date_sample_data_collection 2020-03-09
_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 2.040
_oxdiff_exptl_absorpt_empirical_full_min 0.576