Synthesis of spirocyclic 1,2-diamines by dearomatising intramolecular diamination of phenols.
Aimon, Anthony; Dow, Mark J.; Hanby, Abigail R.; Okolo, Ephraim A.; Pask, Christopher M.; Nelson, Adam; Marsden, Stephen P.; Chemical communications (Cambridge, England) 59 (2023) 607–610; doi:10.1039/d2cc06137f

data_7131094
_publ_section_title
;
 Synthesis of spirocyclic 1,2-diamines by dearomatising intramolecular
 diamination of phenols.
;
_journal_issue                   5
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              607
_journal_page_last               610
_journal_paper_doi               10.1039/d2cc06137f
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety         'C13 H20 N2 O2'
_chemical_formula_sum            'C13 H20 N2 O2'
_chemical_formula_weight         236.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-05-25 deposited with the CCDC.	2022-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.951(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3232(2)
_cell_length_b                   15.4039(3)
_cell_length_c                   9.4930(2)
_cell_measurement_reflns_used    5732
_cell_measurement_temperature    125.01(10)
_cell_measurement_theta_max      73.3160
_cell_measurement_theta_min      5.7400
_cell_volume                     1236.08(5)
_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 0.995
_diffrn_measured_fraction_theta_max 0.976
_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   -112.00 -60.00   1.00    1.00    --  -41.04 -57.00 -60.00   52
  2  \w    -43.00 -13.00   1.00    1.00    --  -41.04 -57.00 -90.00   30
  3  \w    -45.00  32.00   1.00    1.00    --  -41.04  37.00  90.00   77
  4  \w    -64.00  25.00   1.00    1.00    --  -41.04  37.00  30.00   89
  5  \w   -111.00 -22.00   1.00    1.00    --  -41.04 -57.00   0.00   89
  6  \w   -101.00 -67.00   1.00    1.00    --  -41.04 -57.00 -90.00   34
  7  \w     40.00  69.00   1.00    1.00    --   41.04 -57.00 -90.00   29
  8  \w     52.00  78.00   1.00    1.00    --   41.04  57.00   0.00   26
  9  \w     55.00 128.00   1.00    1.00    --  106.02 -15.00 -90.00   73
 10  \w     81.00 108.00   1.00    1.00    --  106.02  30.00   0.00   27
 11  \w     25.00  52.00   1.00    1.00    --  106.02 -15.00 -90.00   27
 12  \w     64.00 103.00   1.00    1.00    --  106.02 -65.00-113.99   39
 13  \w     96.00 144.00   1.00    1.00    --  106.02  45.00 150.00   48
 14  \w     77.00 163.00   1.00    1.00    --  106.02  61.00   0.00   86
 15  \w     94.00 177.00   1.00    1.00    --  106.02  30.00  90.00   83
 16  \w     81.00 118.00   1.00    1.00    --  106.02  45.00   0.00   37
 17  \w     34.00  95.00   1.00    1.00    --  106.02 -65.00  17.17   61
 18  \w    128.00 173.00   1.00    1.00    --  106.02  61.00 -30.00   45
 19  \w     78.00 178.00   1.00    1.00    --  106.02  61.00  30.00  100
 20  \w     76.00 103.00   1.00    1.00    --  106.02 -64.00  34.09   27
 21  \w     77.00 103.00   1.00    1.00    --  106.02  61.00 -30.00   26
 22  \w     35.00 129.00   1.00    1.00    --  106.02 -63.00-168.32   94
 23  \w     61.00  90.00   1.00    1.00    --  106.02 -65.00-126.78   29
 24  \w     41.00 106.00   1.00    1.00    --  106.02 -65.00 -48.86   65
;
_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      -0.0552494000
_diffrn_orient_matrix_UB_12      -0.0950945000
_diffrn_orient_matrix_UB_13      -0.0334993000
_diffrn_orient_matrix_UB_21      -0.1198632000
_diffrn_orient_matrix_UB_22      0.0159695000
_diffrn_orient_matrix_UB_23      0.0699115000
_diffrn_orient_matrix_UB_31      -0.1256331000
_diffrn_orient_matrix_UB_32      0.0265749000
_diffrn_orient_matrix_UB_33      -0.1612743000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            9586
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.541
_diffrn_reflns_theta_min         5.745
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.691
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.623
_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    1.270
_exptl_crystal_description       block
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     160
_refine_ls_number_reflns         2433
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0379
_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^)+(0.0433P)^2^+0.5498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0964
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2188
_reflns_number_total             2433
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc06137f2.cif
_cod_data_source_block           eo104p
_cod_depositor_comments
'Adding full bibliography for 7131091--7131095.cif.'
_cod_database_code               7131094
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C52  H80  N8  O8  '
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.825
_reflns_odcompleteness_completeness 99.35
_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:
 C6(H6), C8(H8), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_olex2_date_sample_data_collection 2019-03-13
_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 1.191
_oxdiff_exptl_absorpt_empirical_full_min 0.868