Regio- and Stereoselective Hydroamination of Alkynes Using an Ammonia Surrogate: Synthesis of N-Silylenamines as Reactive Synthons.
Lui, Erica K. J.; Brandt, Jason W.; Schafer, Laurel L.; Journal of the American Chemical Society 140 (2018) 4973–4976; doi:10.1021/jacs.7b13783

data_4132003
_publ_section_title
;
 Regio- and Stereoselective Hydroamination of Alkynes Using an Ammonia
 Surrogate: Synthesis of N-Silylenamines as Reactive Synthons.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4973
_journal_page_last               4976
_journal_paper_doi               10.1021/jacs.7b13783
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C46 H66 N4 O2 Si Ti'
_chemical_formula_sum            'C46 H66 N4 O2 Si Ti'
_chemical_formula_weight         783.01
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.073(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4428(12)
_cell_length_b                   27.623(3)
_cell_length_c                   13.2015(12)
_cell_measurement_reflns_used    9587
_cell_measurement_temperature    90
_cell_measurement_theta_max      27.123
_cell_measurement_theta_min      2.657
_cell_volume                     4534.5(8)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      90
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'APEX2 DUO'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0337
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            70628
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.180
_diffrn_reflns_theta_min         1.474
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.254
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6353
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0640 before and 0.0463 after correction.
The Ratio of minimum to maximum transmission is 0.8522.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.147
_exptl_crystal_description       prism
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.58
_exptl_crystal_size_mid          0.514
_exptl_crystal_size_min          0.457
_refine_diff_density_max         0.488
_refine_diff_density_min         -0.365
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     502
_refine_ls_number_reflns         10001
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0376
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0354P)^2^+3.3573P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0886
_refine_ls_wR_factor_ref         0.0939
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8630
_reflns_number_total             10001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b13783_si_002.cif
_cod_data_source_block           mo_ls648_0m_a
_cod_original_cell_volume        4534.4(7)
_cod_database_code               4132003
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.866
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 N4(H4), C20(H20), C23(H23), C39(H39), C42(H42)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17), C18(H18),
 C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36), C37(H37)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C01B(H01A,H01B,H01C), C2(H2A,H2B,H2C), C4(H4A,H4B,H4C),
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C017(H01D,H01E,H01F), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              55131
_shelx_hkl_checksum              34017
_olex2_submission_original_sample_id EL06-21
_olex2_submission_special_instructions 'No special instructions were received'