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_7131093
_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         'C20 H26 F N3 O3'
_chemical_formula_sum            'C20 H26 F N3 O3'
_chemical_formula_weight         375.44
_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     direct
_audit_creation_date             2019-01-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-05-26 deposited with the CCDC.	2022-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.566(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6465(3)
_cell_length_b                   19.7846(5)
_cell_length_c                   8.73330(19)
_cell_measurement_reflns_used    3546
_cell_measurement_temperature    120.00(18)
_cell_measurement_theta_max      73.3210
_cell_measurement_theta_min      4.0040
_cell_volume                     1956.20(8)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(18)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.955
_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    -24.00  32.00   1.00    1.00    --  -41.04  37.00   0.00   56
  2  \w    -21.00  30.00   1.00    1.00    --  -41.04  57.00 120.00   51
  3  \w    -68.00  31.00   1.00    1.00    --  -41.04  57.00  60.00   99
  4  \w     43.00  69.00   1.00    1.00    --   41.04 -57.00  30.00   26
  5  \w     15.00  78.00   1.00    1.00    --   41.04  65.00  88.24   63
  6  \w     67.00 105.00   1.00    4.00    --  106.02 -65.00 -17.98   38
  7  \w     26.00 151.00   1.00    4.00    --  106.02 -15.00 -60.00  125
  8  \w     86.00 177.00   1.00    4.00    --  106.02  45.00 120.00   91
  9  \w     34.00 131.00   1.00    4.00    --  106.02 -65.00  35.66   97
 10  \w     56.00  83.00   1.00    4.00    --  106.02 -65.00 -37.16   27
 11  \w     46.00 105.00   1.00    4.00    --  106.02 -63.00 -60.67   59
;
_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      0.0048455000
_diffrn_orient_matrix_UB_12      0.0392025000
_diffrn_orient_matrix_UB_13      -0.1507447000
_diffrn_orient_matrix_UB_21      0.0220761000
_diffrn_orient_matrix_UB_22      0.0661432000
_diffrn_orient_matrix_UB_23      0.0954273000
_diffrn_orient_matrix_UB_31      0.1342070000
_diffrn_orient_matrix_UB_32      -0.0123351000
_diffrn_orient_matrix_UB_33      0.0328450000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0327
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            8404
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.454
_diffrn_reflns_theta_min         3.904
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.766
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.843
_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    1.275
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         3763
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0411P)^2^+0.5017P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0945
_refine_ls_wR_factor_ref         0.1021
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3084
_reflns_number_total             3763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc06137f2.cif
_cod_data_source_block           eo303p
_cod_depositor_comments
'Adding full bibliography for 7131091--7131095.cif.'
_cod_database_code               7131093
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C80  H104  F4  N12  O12  '
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.900
_reflns_odcompleteness_completeness 98.42
_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), C7(H7), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C10(H10A,H10B), C11(H11A,H11B),
 C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C18(H18), C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_olex2_date_sample_data_collection 2019-01-03
_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 1.159
_oxdiff_exptl_absorpt_empirical_full_min 0.938