Catalytic intramolecular hydroamination of aminoallenes using titanium complexes of chiral, tridentate, dianionic imine-diol ligands.
Sha, Fanrui; Mitchell, Benjamin S.; Ye, Christopher Z.; Abelson, Chase S.; Reinheimer, Eric W.; LeMagueres, Pierre; Ferrara, Joseph D.; Takase, Michael K.; Johnson, Adam R.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 9603–9616; doi:10.1039/c8dt05156a

data_7048982
_publ_section_title
;
 Catalytic intramolecular hydroamination of aminoallenes using titanium
 complexes of chiral, tridentate, dianionic imine-diol ligands.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9603
_journal_page_last               9616
_journal_paper_doi               10.1039/c8dt05156a
_journal_volume                  48
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H41 N O2'
_chemical_formula_sum            'C36 H41 N O2'
_chemical_formula_weight         519.70
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5375)
;
_audit_update_record
;
2018-08-28 deposited with the CCDC.
2019-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.77210(10)
_cell_length_b                   11.08970(10)
_cell_length_c                   27.2621(2)
_cell_measurement_reflns_used    24422
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.0940
_cell_measurement_theta_min      4.2770
_cell_volume                     2954.38(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.38b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.38b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.38b (Rigaku OD, 2017)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 HyPix-6000HE
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -58.00 -10.00   0.50    1.20    --  -84.25  19.00 -60.00   96
  2  \w    -71.00  23.00   0.50    0.30    --  -49.03  77.00 120.00  188
  3  \w    -59.00  23.00   0.50    0.30    --  -49.03  37.00  30.00  164
  4  \w     35.00 120.00   0.50    0.30    --   49.03  57.00-120.00  170
  5  \w    102.00 177.00   0.50    1.20    --  105.75 105.00 -78.00  150
  6  \w     34.00 110.00   0.50    1.20    --  105.75 -99.00   0.00  152
  7  \w     34.00 110.00   0.50    1.20    --  105.75 -99.00  60.00  152
  8  \w     33.00  65.00   0.50    1.20    --  105.75 -37.00   0.00   64
  9  \w     33.00  65.00   0.50    1.20    --  105.75 -37.00  30.00   64
 10  \w     34.00 110.00   0.50    1.20    --  105.75 -99.00 -30.00  152
 11  \w     34.00 128.00   0.50    1.20    --  105.75 -77.00-180.00  188
 12  \w     34.00 120.00   0.50    1.20    --  105.75 -57.00-180.00  172
 13  \w     33.00  65.00   0.50    1.20    --  105.75 -37.00-150.00   64
 14  \w   -120.00 -27.00   0.50    0.30    --  -49.03 -77.00  30.00  186
 15  \w   -157.00 -73.00   0.50    1.20    --  -84.25 -37.00-150.00  168
 16  \w   -159.00 -73.00   0.50    1.20    --  -84.25 -19.00 -60.00  172
 17  \w   -159.00 -73.00   0.50    1.20    --  -84.25 -19.00 120.00  172
 18  \w   -156.00-131.00   0.50    1.20    --  -84.25 -57.00  60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0939219000
_diffrn_orient_matrix_UB_12      0.0827243000
_diffrn_orient_matrix_UB_13      -0.0304564000
_diffrn_orient_matrix_UB_21      -0.1198749000
_diffrn_orient_matrix_UB_22      -0.0880356000
_diffrn_orient_matrix_UB_23      0.0079923000
_diffrn_orient_matrix_UB_31      -0.0406949000
_diffrn_orient_matrix_UB_32      0.0686696000
_diffrn_orient_matrix_UB_33      0.0469131000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            27404
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.072
_diffrn_reflns_theta_max         67.072
_diffrn_reflns_theta_min         4.304
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.548
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84240
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.38b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.168
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 2213 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(5)
_refine_ls_extinction_coef       0.00125(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         5277
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0277
_refine_ls_R_factor_gt           0.0272
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0343P)^2^+0.5851P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0683
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5186
_reflns_number_total             5277
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt05156a2.cif
_cod_data_source_block           exp_849_harveymudd_1
_cod_depositor_comments
'Adding full bibliography for 7048978--7048982.cif.'
_cod_database_code               7048982
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C144 H164 N4 O8 '
_reflns_odcompleteness_completeness 99.84
_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. Restrained distances
 C33-C34 \\sim C33-C35 \\sim C33-C36 \\sim C33-C34A \\sim C33-C35A \\sim
C33-C36A
 with sigma of 0.02
 C34-C35 \\sim C34-C36 \\sim C35-C36 \\sim C34A-C35A \\sim C34A-C36A \\sim
C35A-C36A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C34 \\sim C34A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C35 \\sim C35A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C36 \\sim C36A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C35) = Uanis(C35A)
Uanis(C35) = Uanis(C36A)
4. Rigid body (RIGU) restrains
 C34A, H34D, H34E, H34F, C35A, H35D, H35E, H35F, C36A, H36D, H36E, H36F
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35A)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C2(H2A)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
  C26(H26), C28(H28)
6.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C34A(H34D,H34E,H34F),
 C35A(H35D,H35E,H35F), C36A(H36D,H36E,H36F)
;
_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 1.344
_oxdiff_exptl_absorpt_empirical_full_min 0.766