Cp2TiCl2-catalyzed cis-hydroalumination of propargylic amines with Red-Al: stereoselective synthesis of Z-configured allylic amines
Renhong Sun; Jun Liu; Shuang Yang; Ming Chen; Ning Sun; Haoyi Chen; Xin Xie; Xu You; Shi Li; Yuanhong Liu; Chem.Commun. 51 (2015) 6426–; doi:10.1039/C5cc00950B

data_7116894
_publ_section_title
;
 Cp2TiCl2-catalyzed cis-hydroalumination of propargylic amines with
 Red-Al: stereoselective synthesis of Z-configured allylic amines
;
_journal_name_full               Chem.Commun.
_journal_page_first              6426
_journal_paper_doi               10.1039/C5cc00950B
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C16 H26 Al O4 Ti'
_chemical_formula_sum            'C16 H26 Al O4 Ti'
_chemical_formula_weight         357.25
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-08
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2014-12-24 deposited with the CCDC.
2015-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                64.408(2)
_cell_angle_beta                 74.407(2)
_cell_angle_gamma                73.803(2)
_cell_formula_units_Z            2
_cell_length_a                   9.6563(14)
_cell_length_b                   9.8287(14)
_cell_length_c                   10.6494(16)
_cell_measurement_reflns_used    2356
_cell_measurement_temperature    130
_cell_measurement_theta_max      30.24
_cell_measurement_theta_min      2.34
_cell_volume                     862.5(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0244
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            8389
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.524
_diffrn_reflns_theta_min         2.152
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.561
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6558
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0485 before and 0.0333 after correction.
The Ratio of minimum to maximum transmission is 0.8790.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_density_meas      .
_exptl_crystal_description       block
_exptl_crystal_F_000             378
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.364
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         5183
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0657
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0383P)^2^+0.0955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0817
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3793
_reflns_number_total             5183
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc00950b2.cif
_cod_data_source_block           mo_dm14708_0m
_cod_database_code               7116894
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.850
_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 Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              27099
_olex2_submission_special_instructions 'No special instructions were received'