Iridium-catalysed hydroamination of internal homoallylic amines.
Ho, An T.; Vanable, Evan P.; Miguel, Chelsea San; Hull, Kami L.; Chemical communications (Cambridge, England) 60 (2024) 1615–1618; doi:10.1039/d3cc05594a

data_7132585
_publ_section_title
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 Iridium-catalysed hydroamination of internal homoallylic amines.
;
_journal_issue                   12
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1615
_journal_page_last               1618
_journal_paper_doi               10.1039/d3cc05594a
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         '4(C19 H26 N2), 4(C10 H6 O6 S2)'
_chemical_formula_sum            'C116 H128 N8 O24 S8'
_chemical_formula_weight         2274.88
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc22fhkl
_audit_creation_date             2019-05-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-29 deposited with the CCDC.	2024-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.896(2)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   15.6273(6)
_cell_length_b                   11.1454(4)
_cell_length_c                   21.3411(8)
_cell_measurement_reflns_used    12315
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.75
_cell_measurement_theta_min      2.27
_cell_volume                     3592.1(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.9973
_diffrn_measured_fraction_theta_max 0.9973
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0692
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            72162
_diffrn_reflns_theta_full        25.3963
_diffrn_reflns_theta_max         25.40
_diffrn_reflns_theta_min         1.97
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.184
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0684 before and 0.0635 after correction.
The Ratio of minimum to maximum transmission is 0.9057.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.0515
_exptl_crystal_description       prism
_exptl_crystal_F_000             1201.6128
_exptl_crystal_preparation
'1/2 equivalent of Armstrong's Acid was added to 0.05 mmol of the diamine dissolved in 1 mL ethanol. This was then layered with ethyl acetate, and after a weeks time crystals suitable for diffraction were observed.'
_exptl_crystal_recrystallization_method
'Layered crystallization of 0.02 mmol in 0.2 mL ethanol with 0.2 mL fresh ethanol and 0.6 mL ethyl acetate, allowed to sit for two weeks without disturbing to obtain X-ray quality crystals.'
_exptl_crystal_size_max          0.322
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.5014
_refine_diff_density_min         -0.6498
_refine_diff_density_rms         0.0835
_refine_ls_d_res_high            0.8286
_refine_ls_d_res_low             10.3120
_refine_ls_goodness_of_fit_ref   1.0911
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    70
_refine_ls_number_parameters     408
_refine_ls_number_reflns         6586
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.0885
_refine_ls_R_factor_all          0.0713
_refine_ls_R_factor_gt           0.0528
_refine_ls_shift/su_max          0.0002
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0894P)^2^+3.8982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1675
_refine_ls_wR_factor_ref         0.1824
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              18
_reflns_limit_h_min              -18
_reflns_limit_k_max              13
_reflns_limit_k_min              0
_reflns_limit_l_max              25
_reflns_limit_l_min              0
_reflns_number_gt                4856
_reflns_number_total             6586
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3cc05594a3.cif
_cod_data_source_block           dm18o_0m
_cod_depositor_comments
'Adding full bibliography for 7132585--7132586.cif.'
_cod_database_code               7132585
_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 N(H,H) groups, All N(H,H,H) groups
2. Restrained distances
 C22-C1AA \\sim C22-C1AB
 with sigma of 0.02
 C1AA-C2AA \\sim C1AB-C2AB
 with sigma of 0.02
 C1AA-C0AA \\sim C1AB-C0AB
 with sigma of 0.02
 C2AA-C5AA \\sim C2AB-C5AB
 with sigma of 0.02
 C3AA-C5AA \\sim C3AB-C5AB
 with sigma of 0.02
 C3AA-C4AA \\sim C3AB-C4AB
 with sigma of 0.02
 C0AA-C4AA \\sim C0AB-C4AB
 with sigma of 0.02
 C22-C2AA \\sim C22-C2AB
 with sigma of 0.04
 C22-C0AA \\sim C22-C0AB
 with sigma of 0.04
 C1AA-C5AA \\sim C1AB-C5AB
 with sigma of 0.04
 C1AA-C4AA \\sim C1AB-C4AB
 with sigma of 0.04
 C2AA-C3AA \\sim C2AB-C3AB
 with sigma of 0.04
 C2AA-C0AA \\sim C2AB-C0AB
 with sigma of 0.04
 C3AA-C0AA \\sim C3AB-C0AB
 with sigma of 0.04
 C5AA-C4AA \\sim C5AB-C4AB
 with sigma of 0.04
3. Others
 Sof(H22a)=Sof(C2AB)=Sof(H2AB)=Sof(C1AB)=Sof(C0AB)=Sof(H0AB)=Sof(C4AB)=
 Sof(H4AB)=Sof(C3AB)=Sof(H3AB)=Sof(C5AB)=Sof(H5AB)=1-FVAR(1)
 Sof(H22)=Sof(C1AA)=Sof(C2AA)=Sof(H2AA)=Sof(C3AA)=Sof(H3AA)=Sof(C0AA)=
 Sof(H0AA)=Sof(C5AA)=Sof(H5AA)=Sof(C4AA)=Sof(H4AA)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C22(H22), C22(H22a), C23(H23), C25(H25)
4.b Secondary CH2 refined with riding coordinates:
 N2(H2a,H2b), C24(H24a,H24b), C32(H32a,H32b), C33(H33a,H33b), C34(H34a,H34b)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C10(H10), C9(H9), C8(H8),
 C5(H5), C6(H6), C7(H7), C2AA(H2AA), C3AA(H3AA), C0AA(H0AA), C5AA(H5AA),
 C4AA(H4AA), C2AB(H2AB), C0AB(H0AB), C4AB(H4AB), C3AB(H3AB), C5AB(H5AB)
4.d Idealised Me refined as rotating group:
 N1(H1a,H1b,H1c)
;
_olex2_date_sample_data_collection 2018-12-14
_olex2_date_sample_submission    2018-12-13
_olex2_exptl_crystal_mounting_method
'The crystals were mounted on a loop using paratone oil.'
_olex2_submission_original_sample_id dm18o_0m
_olex2_submission_special_instructions 'No special instructions were received'