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_7131095
_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         'C17 H18 N2 O4 S, 0.06(H2 O)'
_chemical_formula_sum            'C17 H18.12 N2 O4.06 S'
_chemical_formula_weight         347.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-01
_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                 91.007(7)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   21.9810(18)
_cell_length_b                   8.5032(5)
_cell_length_c                   34.011(3)
_cell_measurement_reflns_used    1508
_cell_measurement_temperature    125.01(10)
_cell_measurement_theta_max      73.4040
_cell_measurement_theta_min      3.9680
_cell_volume                     6356.0(9)
_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 0.998
_diffrn_measured_fraction_theta_max 0.973
_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 -16.00   1.00   30.00    --  -40.79 -37.00  30.00   96
  2  \w    -64.00  28.00   1.00   30.00    --  -40.79  37.00-150.00   92
  3  \w     30.00  88.00   1.00   30.00    --   40.79  19.00 -30.00   58
  4  \w     97.00 132.00   1.00  120.00    --  106.02 -45.00  30.00   35
  5  \w     95.00 178.00   1.00  120.00    --  106.02  30.00 120.00   83
  6  \w     44.00 108.00   1.00  120.00    --  106.02 -61.00  60.00   64
  7  \w     77.00 176.00   1.00  120.00    --  106.02  61.00-180.00   99
  8  \w     79.00 144.00   1.00  120.00    --  106.02  61.00-120.00   65
  9  \w     30.00  88.00   1.00  120.00    --  106.02 -30.00-120.00   58
 10  \w     33.00  63.00   1.00  120.00    --  106.02 -45.00  30.00   30
;
_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      0.0258272000
_diffrn_orient_matrix_UB_12      -0.0753775000
_diffrn_orient_matrix_UB_13      0.0379393000
_diffrn_orient_matrix_UB_21      -0.0283181000
_diffrn_orient_matrix_UB_22      0.1329932000
_diffrn_orient_matrix_UB_23      0.0244221000
_diffrn_orient_matrix_UB_31      -0.0586798000
_diffrn_orient_matrix_UB_32      -0.0973121000
_diffrn_orient_matrix_UB_33      0.0040186000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0862
_diffrn_reflns_av_unetI/netI     0.1321
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            12352
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.543
_diffrn_reflns_theta_min         4.023
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.037
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.744
_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    1.453
_exptl_crystal_description       needle
_exptl_crystal_F_000             2922
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.451
_refine_diff_density_min         -0.580
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     436
_refine_ls_number_reflns         6240
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1395
_refine_ls_R_factor_gt           0.0771
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0671P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1679
_refine_ls_wR_factor_ref         0.2158
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3479
_reflns_number_total             6240
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc06137f2.cif
_cod_data_source_block           eo194p
_cod_depositor_comments
'Adding full bibliography for 7131091--7131095.cif.'
_cod_original_cell_volume        6355.9(8)
_cod_database_code               7131095
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C272  H290  N32  O65  S16  '
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.663
_reflns_odcompleteness_completeness 99.85
_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. Others
 Fixed Sof: O9(0.125)
3.a Ternary CH refined with riding coordinates:
 C2(H2), C19(H19)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C20(H20A,H20B), C24(H24A,
 H24B), C25(H25A,H25B), C26(H26A,H26B)
3.c Me refined with riding coordinates:
 C17(H17A,H17B,H17C)
3.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C12(H12), C13(H13), C15(H15), C16(H16), C22(H22), C23(H23),
 C29(H29), C30(H30), C32(H32), C33(H33)
3.e Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C)
;
_olex2_date_sample_data_collection 2019-02-25
_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 1.270
_oxdiff_exptl_absorpt_empirical_full_min 0.700