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_7127655
_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         'C8 H17 N2 O2 S'
_chemical_formula_sum            'C8 H17 N2 O2 S'
_chemical_formula_weight         205.29
_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     dual
_audit_creation_date             2019-04-09
_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                 104.737(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4270(10)
_cell_length_b                   13.1722(12)
_cell_length_c                   9.2077(10)
_cell_measurement_reflns_used    2389
_cell_measurement_temperature    125.01(10)
_cell_measurement_theta_max      72.2620
_cell_measurement_theta_min      5.9770
_cell_volume                     988.45(19)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_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      125.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_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   -114.00 -19.00   1.00   15.00    --  -40.79 -57.00-120.00   95
  2  \w    -69.00  27.00   1.00   15.00    --  -40.79  57.00  30.00   96
  3  \w     20.00  69.00   1.00   15.00    --   40.79 -64.00  53.25   49
  4  \w     11.00  37.00   1.00   15.00    --   40.79  64.00 -38.75   26
  5  \w     36.00  71.00   1.00   15.00    --   40.79 -65.00  12.36   35
  6  \w    -15.00  12.00   1.00   15.00    --   40.79 -62.00  95.40   27
  7  \w    -16.00  67.00   1.00   15.00    --   40.79 -65.00 153.76   83
  8  \w     34.00  61.00   1.00   15.00    --   40.79 -62.00  95.40   27
  9  \w     70.00 112.00   1.00   15.00    --   40.79  64.00 -38.75   42
 10  \w     46.00  71.00   1.00   15.00    --   40.79 -65.00 -65.55   25
 11  \w     69.00  96.00   1.00   60.00    --  106.02 -65.00-123.20   27
 12  \w     33.00  96.00   1.00   60.00    --  106.02 -65.00 -72.94   63
 13  \w     68.00 134.00   1.00   60.00    --  106.02 -30.00  60.00   66
 14  \w     55.00 100.00   1.00   60.00    --  106.02 -65.00-141.98   45
 15  \w     42.00 103.00   1.00   60.00    --  106.02 -65.00  98.58   61
 16  \w     70.00 123.00   1.00   60.00    --  106.02 -65.00 169.15   53
 17  \w     73.00 100.00   1.00   60.00    --  106.02 -65.00 -52.96   27
 18  \w     80.00 177.00   1.00   60.00    --  106.02  45.00 120.00   97
 19  \w     81.00 134.00   1.00   60.00    --  106.02  45.00-120.00   53
 20  \w     66.00  95.00   1.00   60.00    --  106.02 -65.00 137.15   29
 21  \w     39.00  92.00   1.00   60.00    --  106.02 -65.00 -12.20   53
 22  \w     65.00  90.00   1.00   60.00    --  106.02 -65.00 -92.55   25
 23  \w     79.00 177.00   1.00   60.00    --  106.02  61.00  60.00   98
 24  \w     67.00  94.00   1.00   60.00    --  106.02 -65.00  59.89   27
 25  \w     79.00 152.00   1.00   60.00    --  106.02  30.00  30.00   73
 26  \w     70.00 105.00   1.00   60.00    --  106.02 -65.00  11.13   35
 27  \w     69.00  96.00   1.00   60.00    --  106.02 -65.00  43.16   27
;
_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      -0.1886124000
_diffrn_orient_matrix_UB_12      0.0062135000
_diffrn_orient_matrix_UB_13      -0.0482501000
_diffrn_orient_matrix_UB_21      -0.0022718000
_diffrn_orient_matrix_UB_22      0.0289035000
_diffrn_orient_matrix_UB_23      0.1616921000
_diffrn_orient_matrix_UB_31      0.0110250000
_diffrn_orient_matrix_UB_32      0.1131351000
_diffrn_orient_matrix_UB_33      -0.0385823000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            3369
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.650
_diffrn_reflns_theta_min         5.428
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.693
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_correction_T_min  0.626
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
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    1.380
_exptl_crystal_description       needle
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.577
_refine_diff_density_min         -0.590
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         3369
_refine_ls_number_restraints     203
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0947
_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^)+(0.1318P)^2^+0.0586P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2024
_refine_ls_wR_factor_ref         0.2113
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2464
_reflns_number_total             3369
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9320\% 
 around [-0.23 -0.00 0.97] (reciprocal) or [-0.00 0.00 1.00] (direct)
;
_cod_data_source_file            d0cc07625b2.cif
_cod_data_source_block           sg_2_64_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 7127654--7127656.cif.'
_cod_database_code               7127655
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C32  H68  N8  O8  S4  '
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.428
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.549(3)
 0.451(3)
2. 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
3. Restrained distances
 N1A-H1A
 1 with sigma of 0.01
 N1B-H1B
 1 with sigma of 0.01
4. Rigid body (RIGU) restrains
 C8B, S1, N2, N1A, N1B, O1, O2, O2A, O1A, C3A, C3B, C7A, C7B, C1A, C1B, C2,
 C4A, C4B, C6, C8A, C5A, C5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H2AA(0.5) H2AB(0.5) H2BC(0.5) H2BD(0.5) H6AA(0.5) H6AB(0.5)
 H6BC(0.5) H6BD(0.5) C8B(0.5) H8BA(0.5) H8BB(0.5) H8BC(0.5) N1A(0.5) C3A(0.5)
 H3A(0.5) N1B(0.5) C3B(0.5) H3B(0.5) C5A(0.5) H5AA(0.5) H5AB(0.5) C5B(0.5)
 H5BA(0.5) H5BB(0.5) C1A(0.5) H1AA(0.5) C4B(0.5) H4BA(0.5) H4BB(0.5) C4A(0.5)
 H4AA(0.5) H4AB(0.5) C1B(0.5) H1BA(0.5) O1(0.5) O2(0.5) O2A(0.5) O1A(0.5)
 C7A(0.5) H7AA(0.5) H7AB(0.5) C7B(0.5) H7BA(0.5) H7BB(0.5) C8A(0.5) H8AA(0.5)
 H8AB(0.5) H8AC(0.5)
6.a Ternary CH refined with riding coordinates:
 C3A(H3A), C3B(H3B), C1A(H1AA), C1B(H1BA)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2AA,H2AB), C2(H2BC,H2BD), C6(H6AA,H6AB), C6(H6BC,H6BD), C5A(H5AA,H5AB),
 C5B(H5BA,H5BB), C4B(H4BA,H4BB), C4A(H4AA,H4AB), C7A(H7AA,H7AB), C7B(H7BA,H7BB)
6.c Idealised Me refined as rotating group:
 C8B(H8BA,H8BB,H8BC), C8A(H8AA,H8AB,H8AC)
;
_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 1.919
_oxdiff_exptl_absorpt_empirical_full_min 0.509
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2