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_7132586
_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_absolute_configuration ad
_chemical_formula_moiety         '2(C7 H7 O3 S), C17 H28 N2 O'
_chemical_formula_sum            'C31 H42 N2 O7 S2'
_chemical_formula_weight         618.78
_chemical_name_systematic
'4-(3-(ammonio(phenyl)methyl)cyclohexyl)morpholin-4-ium bis-(4-methylphenylsulfonate)'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2gj4pv
_audit_creation_date             2018-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-07-05 deposited with the CCDC.	2024-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1123(4)
_cell_length_b                   11.2096(4)
_cell_length_c                   24.9678(9)
_cell_measurement_reflns_used    28796
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      28.29
_cell_measurement_theta_min      2.44
_cell_volume                     3110.10(19)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0427
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            77713
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.303
_diffrn_reflns_theta_min         2.442
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.220
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7011
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.0606 before and 0.0551 after correction. The Ratio of minimum to maximum transmission is 0.9402. 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    1.322
_exptl_crystal_description       prism
_exptl_crystal_F_000             1320
_exptl_crystal_preparation
'The free amine (0.54 mmol) was mixed with 2.1 equivalents of PTSA*H2O in 1.5 mL absolute ethanol. This was stirred for 5 minutes, then crystallizations were set up.'
_exptl_crystal_recrystallization_method
'A layered crystallization was performed in a flame-sealed pipette. 0.5 mL of the aforementioned solution was placed into a pipette, another 0.3 mL ethanol layered onto it carefully, and 1.5 mL diethyl ether layered onto that. After 10 days large high quality crystals had formed.'
_exptl_crystal_size_max          0.529
_exptl_crystal_size_mid          0.475
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.290
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 3219 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         7735
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0292
_refine_ls_R_factor_gt           0.0275
_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^)+(0.0448P)^2^+0.6154P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0723
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.788
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                7454
_reflns_number_total             7735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05594a3.cif
_cod_data_source_block           dm70n_0m
_cod_depositor_comments
'Adding full bibliography for 7132585--7132586.cif.'
_cod_database_code               7132586
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.892
_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, All N(H) groups, All N(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 N2(H2), C1(H1), C2(H2A), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C14(H14A,H14B), C15(H15A,
 H15B), C16(H16A,H16B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C22(H22), C23(H23), C26(H26), C27(H27), C29(H29),
 C30(H30), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C31(H31A,H31B,H31C), N1(H1A,H1B,H1C)
;
_shelx_res_checksum              42067
_shelx_hkl_checksum              9796
_olex2_exptl_crystal_mounting_method
'Paratone oil was used for mounting on a thin metal loop. '
_olex2_submission_original_sample_id ev-e-1357-cy-morph
_olex2_submission_special_instructions 'No special instructions were received'