Regioselective side-chain amination of 2-alkyl azacycles by radical translocation: total synthesis of tetraponerine T8.
Griggs, Samuel D.; Martin-Roncero, Alejandro; Nelson, Adam; Marsden, Stephen P.; Chemical communications (Cambridge, England) 57 (2021) 919–922; doi:10.1039/d0cc07625b

data_7127656
_publ_section_title
;
 Regioselective side-chain amination of 2-alkyl azacycles by radical
 translocation: total synthesis of tetraponerine T8.
;
_journal_issue                   7
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              919
_journal_page_last               922
_journal_paper_doi               10.1039/d0cc07625b
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C9 H17 N2 O3 S'
_chemical_formula_sum            'C9 H17 N2 O3 S'
_chemical_formula_weight         233.30
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-11-19 deposited with the CCDC.	2020-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.005(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.3294(5)
_cell_length_b                   20.3329(14)
_cell_length_c                   12.2453(9)
_cell_measurement_reflns_used    3699
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      71.0350
_cell_measurement_theta_min      4.1910
_cell_volume                     2305.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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    -64.00  33.00   1.00   20.00    --  -40.29  57.00-120.00   97
  2  \w   -112.00 -18.00   1.00   20.00    --  -40.29 -57.00  90.00   94
  3  \w     18.00  45.00   1.00   20.00    --   40.29  57.00  90.00   27
  4  \w     87.00 176.00   1.00   80.00    --  103.83  30.00 -90.00   89
  5  \w     91.00 123.00   1.00   80.00    --  103.83  61.00  60.00   32
  6  \w    148.00 175.00   1.00   80.00    --  103.83  61.00  60.00   27
  7  \w     32.00 109.00   1.00   80.00    --  103.83 -45.00  30.00   77
  8  \w     47.00 100.00   1.00   80.00    --  103.83 -61.00 120.00   53
  9  \w    138.00 168.00   1.00   80.00    --  103.83  61.00   0.00   30
 10  \w     97.00 177.00   1.00   80.00    --  103.83  45.00-180.00   80
 11  \w     48.00 133.00   1.00   80.00    --  103.83 -64.00 162.10   85
 12  \w    -64.00  -3.00   1.00   20.00    --  -40.29 -19.00  90.00   61
 13  \w     28.00  67.00   1.00   20.00    --   40.29 -57.00-120.00   39
 14  \w     14.00  41.00   1.00   20.00    --   40.29  65.00-130.82   27
 15  \w     11.00  53.00   1.00   20.00    --   40.29  64.00  53.80   42
 16  \w     38.00  65.00   1.00   20.00    --   40.29 -57.00  30.00   27
 17  \w     11.00  41.00   1.00   20.00    --   40.29  65.00 -45.09   30
 18  \w     14.00  46.00   1.00   20.00    --   40.29 -57.00 -60.00   32
 19  \w    113.00 176.00   1.00   80.00    --  103.83  61.00 120.00   63
 20  \w     64.00 126.00   1.00   80.00    --  103.83 -65.00 -59.87   62
 21  \w     72.00  99.00   1.00   80.00    --  103.83 -65.00-173.62   27
 22  \w    126.00 153.00   1.00   80.00    --  103.83  45.00 -30.00   27
 23  \w     80.00 108.00   1.00   80.00    --  103.83  45.00 -30.00   28
 24  \w     61.00 108.00   1.00   80.00    --  103.83 -65.00-140.50   47
 25  \w     77.00 104.00   1.00   80.00    --  103.83 -65.00  98.10   27
 26  \w     93.00 132.00   1.00   80.00    --  103.83 -64.00  43.01   39
 27  \w     79.00 106.00   1.00   80.00    --  103.83 -65.00   8.83   27
 28  \w     31.00 111.00   1.00   80.00    --  103.83 -65.00 -12.23   80
 29  \w     69.00  99.00   1.00   80.00    --  103.83 -65.00 -96.81   30
 30  \w     61.00  91.00   1.00   80.00    --  103.83 -65.00 143.90   30
 31  \w     83.00 108.00   1.00   80.00    --  103.83 -64.00 -36.24   25
 32  \w     53.00  96.00   1.00   80.00    --  103.83 -65.00  70.38   43
;
_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      0.0050631000
_diffrn_orient_matrix_UB_12      0.0590157000
_diffrn_orient_matrix_UB_13      -0.0782027000
_diffrn_orient_matrix_UB_21      -0.1147444000
_diffrn_orient_matrix_UB_22      0.0355546000
_diffrn_orient_matrix_UB_23      0.0588311000
_diffrn_orient_matrix_UB_31      0.1204114000
_diffrn_orient_matrix_UB_32      0.0313827000
_diffrn_orient_matrix_UB_33      0.0806617000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0957
_diffrn_reflns_av_unetI/netI     0.0703
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            19681
_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         72.853
_diffrn_reflns_theta_min         4.238
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.446
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.723
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.344
_exptl_crystal_description       needle
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.707
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         4497
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.1114
_refine_ls_R_factor_gt           0.0818
_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^)+(0.0826P)^2^+3.6103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1841
_refine_ls_wR_factor_ref         0.2002
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3293
_reflns_number_total             4497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07625b2.cif
_cod_data_source_block           sg_5_52
_cod_depositor_comments
'Adding full bibliography for 7127654--7127656.cif.'
_cod_database_code               7127656
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C72  H136  N16  O24  S8  '
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.667
_reflns_odcompleteness_completeness 99.95
_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:
 C4(H4), C6(H6), C13(H13), C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B), C16(H16A,H16B), C17(H17A,H17B),
  C18(H18A,H18B)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C10(H10A,H10B,H10C)
;
_olex2_date_sample_data_collection 2020-02-18
_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 1.529
_oxdiff_exptl_absorpt_empirical_full_min 0.579