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_4135132
_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         'C17 H21 N2 O, 1(C2 F3 O2)'
_chemical_formula_sum            'C19 H21 F3 N2 O3'
_chemical_formula_weight         382.38
_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             2020-03-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                91.790(17)
_cell_angle_beta                 97.291(19)
_cell_angle_gamma                102.179(17)
_cell_formula_units_Z            2
_cell_length_a                   7.5941(10)
_cell_length_b                   11.684(3)
_cell_length_c                   11.764(3)
_cell_measurement_reflns_used    31
_cell_measurement_temperature    120
_cell_measurement_theta_max      3
_cell_measurement_theta_min      22
_cell_volume                     1010.3(4)
_computing_cell_refinement       'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_computing_data_reduction        'EvalCCD (Duisenberg & Schreurs, 1990-2000)'
_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_temperature      120
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0734
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12067
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.574
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_exptl_absorpt_coefficient_mu    0.103
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5536
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1024 before and 0.0731 after correction.
The Ratio of minimum to maximum transmission is 0.7425.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       prism
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.485
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         4566
_refine_ls_number_restraints     325
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1338
_refine_ls_R_factor_gt           0.0741
_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^)+(0.1039P)^2^+0.2716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1818
_refine_ls_wR_factor_ref         0.2212
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2529
_reflns_number_total             4566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05804_si_017.cif
_cod_data_source_block           randres-3rat83p2
_cod_database_code               4135132
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.978
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F4-F5 \\sim F4-F6 \\sim F5-F6
 with sigma of 0.02
 F4-C20 \\sim F5-C20 \\sim F6-C20 \\sim F1-C19 \\sim F2-C19 \\sim F3-C19
 with sigma of 0.02
 O2-C18 \\sim O3-C18 \\sim O4-C23 \\sim O5-C23
 with sigma of 0.02
 C19-C18 \\sim C23-C20
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C18 \\sim O3 \\sim O2 \\sim C19 \\sim F3 \\sim F1 \\sim F2 \\sim F6 \\sim O4
\\sim C23 \\sim O5 \\sim C20 \\sim F4 \\sim F5: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 C19, O3, C18, O2, F3, F1, F2, C20, O4, C23, O5, F4, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O4)=Sof(O5)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(C20)=Sof(C23)=1-FVAR(1)
 Sof(O3)=Sof(O2)=Sof(C18)=Sof(C19)=Sof(F3)=Sof(F1)=Sof(F2)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 N2(H2), C15(H15)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C9(H9A,H9B), C13(H13A,H13B), C12(H12A,H12B)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C3(H3), C4(H4)
6.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              97059
_shelx_hkl_checksum              8469
_shelx_fab_checksum              47116
_olex2_submission_special_instructions 'No special instructions were received'