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_1571247
_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         '0.63(H2 O), 0.37(C H4 O), C17 H20 N2'
_chemical_formula_sum            'C17.36 H22.73 N2 O'
_chemical_formula_weight         275.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc2h5h7f
_audit_creation_date             2022-12-08
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.11.02 svn.ra8b101fa for OlexSys, GUI svn.r6635)
;
_audit_update_record
;
2023-10-04 deposited with the CCDC.	2024-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.275(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1586(3)
_cell_length_b                   21.5030(8)
_cell_length_c                   8.6653(3)
_cell_measurement_reflns_used    3229
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.8430
_cell_measurement_theta_min      5.4380
_cell_volume                     1513.75(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3577
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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     29.00  90.00   1.00   13.00    --  112.00 -94.00-120.00   61
  2  \w   -121.00   0.00   1.00    7.00    --  -40.88 -19.00  60.00  121
  3  \w    -16.00  72.00   1.00    7.00    --   40.88 -77.00-120.00   88
  4  \w     18.00 114.00   1.00    7.00    --   40.88  37.00  30.00   96
  5  \w     40.00 100.00   1.00    7.00    --   40.88-133.00 140.00   60
  6  \w     90.00 178.00   1.00   13.00    --  112.00  30.00   0.00   88
  7  \w    103.00 177.00   1.00   13.00    --  112.00  77.00  90.00   74
  8  \w     36.00 100.00   1.00   13.00    --  112.00 -94.00   0.00   64
  9  \w     85.00 175.00   1.00   13.00    --  112.00  30.00  60.00   90
 10  \w     71.00 109.00   1.00   13.00    --  112.00-111.00 120.00   38
 11  \w     65.00 146.00   1.00   13.00    --  112.00 178.00 -90.00   81
 12  \w     39.00 109.00   1.00   13.00    --  112.00-111.00 -60.00   70
 13  \w     39.00 138.00   1.00   13.00    --  112.00 -45.00  30.00   99
 14  \w     49.00 109.00   1.00   13.00    --  112.00 -61.00 -30.00   60
;
_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      0.0139393000
_diffrn_orient_matrix_UB_12      -0.0713510000
_diffrn_orient_matrix_UB_13      0.0101638000
_diffrn_orient_matrix_UB_21      0.1444541000
_diffrn_orient_matrix_UB_22      0.0063201000
_diffrn_orient_matrix_UB_23      0.1265943000
_diffrn_orient_matrix_UB_31      -0.1221140000
_diffrn_orient_matrix_UB_32      -0.0007053000
_diffrn_orient_matrix_UB_33      0.1254729000
_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  0.0448
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            9746
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.790
_diffrn_reflns_theta_min         5.445
_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    0.588
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75294
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
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    1.209
_exptl_crystal_description       plate
_exptl_crystal_F_000             596
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.317
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         3132
_refine_ls_number_restraints     129
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0540
_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^)+(0.0691P)^2^+0.6338P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1389
_refine_ls_wR_factor_ref         0.1506
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2462
_reflns_number_total             3132
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00601a1.cif
_cod_data_source_block           fma5cult_auto
_cod_depositor_comments
'Adding full bibliography for 1571247--1571248.cif.'
_cod_original_cell_volume        1513.75(9)
_cod_database_code               1571247
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C12 H10 N2 '
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.933
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 C13A-C15A \\sim C13A-C15
 with sigma of 0.02
 N2-C14A \\sim N2-C6A
 with sigma of 0.02
 N2-C13A \\sim N2-C7A
 with sigma of 0.04
 C15A-C16A \\sim C15-C16
 with sigma of 0.02
 C13A-C16A \\sim C13A-C16
 with sigma of 0.04
 C13A-C15A \\sim C7A-C15A
 with sigma of 0.02
 C14A-C15A \\sim C6A-C15A
 with sigma of 0.04
 C13A-C14A \\sim C7A-C6A
 with sigma of 0.02
 C13A-C12 \\sim C7A-C12
 with sigma of 0.02
 C13A-C15 \\sim C7A-C15
 with sigma of 0.02
 C14A-C12 \\sim C6A-C12
 with sigma of 0.04
 C14A-C15 \\sim C6A-C15
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O1S) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C14A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C15A) \\sim Ueq,
Uanis(C16A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C12) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(O1W) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
4. Rigid body (RIGU) restrains
 O1S
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13A, C15, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C12, C13A, C14A, C15A, C16A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C6A, C7A, C12, C15, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1W
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: O1W(0.63) H1WA(0.63) H1WB(0.63) O1S(0.37) H1S(0.37) C1S(0.37)
 H1SA(0.37) H1SB(0.37) H1SC(0.37) C6A(0.5) H6AA(0.5) H6AB(0.5) C7A(0.5)
 H12A(0.5) H12B(0.5) H12C(0.5) H12D(0.5) C13A(0.5) C14A(0.5) H14A(0.5)
 H14B(0.5) C15A(0.5) H15A(0.5) C15(0.5) H15(0.5) C16A(0.5) H16A(0.5) H16B(0.5)
 H16C(0.5) C16(0.5) H16D(0.5) H16E(0.5) H16F(0.5)
6.a Riding coordinates:
 O1S(H1S), N1(H1), N2(H2)
6.b Free rotating group:
 O1W(H1WA,H1WB)
6.c Ternary CH refined with riding coordinates:
 C8(H8), C9(H9)
6.d Secondary CH2 refined with riding coordinates:
 C6A(H6AA,H6AB), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C12(H12C,
 H12D), C14A(H14A,H14B)
6.e Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C15A(H15A), C15(H15)
6.f Idealised Me refined as rotating group:
 C1S(H1SA,H1SB,H1SC), C16A(H16A,H16B,H16C), C16(H16D,H16E,H16F)
;
_shelx_res_checksum              70240
_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 1.380
_oxdiff_exptl_absorpt_empirical_full_min 0.764