Aza-Achmatowicz rearrangement coupled with intermolecular aza-Friedel-Crafts enables total syntheses of uleine and aspidosperma alkaloids.
Ma, Foqing; Li, Yunlong; Akkarasereenon, Kornkamon; Qiu, Huiying; Cheung, Yuen Tsz; Guo, Zhihong; Tong, Rongbiao; Chemical science 15 (2024) 5730–5737; doi:10.1039/d4sc00601a

data_1571248
_publ_section_title
;
 Aza-Achmatowicz rearrangement coupled with intermolecular
 aza-Friedel-Crafts enables total syntheses of uleine and aspidosperma
 alkaloids.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              5730
_journal_page_last               5737
_journal_paper_doi               10.1039/d4sc00601a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C18 H22 N2 O3'
_chemical_formula_sum            'C18 H22 N2 O3'
_chemical_formula_weight         314.37
_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     iterative
_audit_creation_date             2021-08-26
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6392)
;
_audit_update_record
;
2023-10-04 deposited with the CCDC.	2024-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                83.313(5)
_cell_angle_beta                 81.185(5)
_cell_angle_gamma                61.479(6)
_cell_formula_units_Z            2
_cell_length_a                   8.9869(6)
_cell_length_b                   9.3453(5)
_cell_length_c                   11.1740(6)
_cell_measurement_reflns_used    3096
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.3310
_cell_measurement_theta_min      4.0010
_cell_volume                     813.81(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1788
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.954
_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     92.00 176.00   1.00    3.00    --  113.00  30.00   0.00   84
  2  \w    -59.00  -7.00   1.00    1.50    --  -39.95 125.00-120.00   52
  3  \w   -116.00 -16.00   1.00    1.50    --  -39.95 -37.00  60.00  100
  4  \w   -113.00 -28.00   1.00    1.50    --  -39.95 -37.00 -30.00   85
  5  \w    -77.00  -6.00   1.00    1.50    --  -39.95 125.00 150.00   71
  6  \w     53.00  97.00   1.00    1.50    --   39.95-125.00  60.00   44
  7  \w     36.00 108.00   1.00    3.00    --  113.00-111.00  30.00   72
  8  \w    104.00 176.00   1.00    3.00    --  113.00 111.00-180.00   72
  9  \w     64.00 109.00   1.00    3.00    --  113.00-111.00 120.00   45
 10  \w     36.00  63.00   1.00    3.00    --  113.00-111.00 120.00   27
 11  \w     35.00 107.00   1.00    3.00    --  113.00 -94.00-150.00   72
 12  \w     85.00 168.00   1.00    3.00    --  113.00  45.00 -60.00   83
 13  \w     85.00 177.00   1.00    3.00    --  113.00  45.00-120.00   92
 14  \w     47.00 138.00   1.00    3.00    --  113.00 -61.00-150.00   91
 15  \w     51.00 122.00   1.00    3.00    --  113.00 -45.00  60.00   71
;
_diffrn_measurement_device       'kappa 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      0.1375284000
_diffrn_orient_matrix_UB_12      -0.1658001000
_diffrn_orient_matrix_UB_13      0.0460295000
_diffrn_orient_matrix_UB_21      -0.0235061000
_diffrn_orient_matrix_UB_22      0.0712600000
_diffrn_orient_matrix_UB_23      0.1232025000
_diffrn_orient_matrix_UB_31      -0.1381294000
_diffrn_orient_matrix_UB_32      -0.0521614000
_diffrn_orient_matrix_UB_33      0.0470785000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0161
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5008
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.729
_diffrn_reflns_theta_min         4.008
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.710
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85793
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         3272
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0346
_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^)+(0.0441P)^2^+0.2115P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0866
_refine_ls_wR_factor_ref         0.0907
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2924
_reflns_number_total             3272
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00601a1.cif
_cod_data_source_block           fma4cult_auto
_cod_depositor_comments
'Adding full bibliography for 1571247--1571248.cif.'
_cod_database_code               1571248
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.901
_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.a Ternary CH refined with riding coordinates:
 C2(H2A), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C4(H4), C11(H11), C14(H14), C15(H15), C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              13572
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.408
_oxdiff_exptl_absorpt_empirical_full_min 0.831