Exploiting natural complexity for substrate controlled regioselectivity and stereoselectivity in tantalum catalysed hydroaminoalkylation
Zheng, Cameron H. M.; Nadeau, Ben E.; Trajano, Heather L.; Schafer, Laurel L.; Green Chemistry 26 (2024) 9729–9736; doi:10.1039/D4GC01614A

data_7249255
_publ_section_title
;
 Exploiting natural complexity for substrate controlled regioselectivity
 and stereoselectivity in tantalum catalysed hydroaminoalkylation
;
_journal_issue                   18
_journal_name_full               'Green Chemistry'
_journal_page_first              9729
_journal_page_last               9736
_journal_paper_doi               10.1039/D4GC01614A
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         '2(Cl), 2(C22 H34 N)'
_chemical_formula_sum            'C44 H68 Cl2 N2'
_chemical_formula_weight         695.90
_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_creation_date             2024-03-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-29 deposited with the CCDC.	2024-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0051(6)
_cell_length_b                   18.9291(14)
_cell_length_c                   36.914(3)
_cell_measurement_reflns_used    1731
_cell_measurement_temperature    100
_cell_measurement_theta_max      39.55
_cell_measurement_theta_min      2.39
_cell_volume                     4894.8(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1460
_diffrn_reflns_av_unetI/netI     0.1045
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            13495
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        40.018
_diffrn_reflns_theta_max         40.018
_diffrn_reflns_theta_min         2.394
_diffrn_source_current           0.59
_diffrn_source_power             0.026367099999999997
_diffrn_source_voltage           44.69
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.375
_exptl_absorpt_correction_T_max  0.7479
_exptl_absorpt_correction_T_min  0.5570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0948 before and 0.0702 after correction.
The Ratio of minimum to maximum transmission is 0.7448.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.944
_exptl_crystal_description       block
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.875
_refine_diff_density_min         -0.456
_refine_diff_density_rms         0.190
_refine_ls_abs_structure_details
;
 Flack x determined using 485 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(5)
_refine_ls_extinction_coef       0.0051(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.305
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         2936
_refine_ls_number_restraints     222
_refine_ls_restrained_S_all      1.256
_refine_ls_R_factor_all          0.1935
_refine_ls_R_factor_gt           0.1423
_refine_ls_shift/su_max          0.888
_refine_ls_shift/su_mean         0.017
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3421
_refine_ls_wR_factor_ref         0.3828
_reflns_Friedel_coverage         0.670
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                1793
_reflns_number_total             2936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc01614a2.cif
_cod_data_source_block           cu_ls1009_0m
_cod_depositor_comments
'Adding full bibliography for 7249254--7249255.cif.'
_cod_database_code               7249255
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.922
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C10 \\sim N1 \\sim C2 \\sim C1 \\sim C7 \\sim C3 \\sim C8 \\sim C6 \\sim C4
\\sim C17 \\sim C16 \\sim C9 \\sim C5 \\sim C15 \\sim C14 \\sim C11 \\sim C13
\\sim C20 \\sim C12 \\sim C19 \\sim C21 \\sim C22 \\sim C18: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C28) = Uanis(C27) = Uanis(C26) = Uanis(C25) = Uanis(C24) = Uanis(C29)
Uanis(C3) = Uanis(C4) = Uanis(C5) = Uanis(C6) = Uanis(C7) = Uanis(C2)
Uanis(C22) = Uanis(C20) = Uanis(C21) = Uanis(C19) = Uanis(C14) = Uanis(C1)
Uanis(C13) = Uanis(C14)
Uanis(C15) = Uanis(C14)
Uanis(C16) = Uanis(C15)
Uanis(C11) = Uanis(C13)
Uanis(C12) = Uanis(C11)
Uanis(C8) = Uanis(C16)
Uanis(C9) = Uanis(C8)
Uanis(C18) = Uanis(C12)
Uanis(C10) = Uanis(C11)
3. Rigid body (RIGU) restrains
 C28, C27, C26, C24, C29, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, C7, C6, C5, C4, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C13(H13), C14(H14), C35(H35), C36(H36)
4.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), C38(H38A,H38B), C16(H16A,H16B), C1(H1C,H1D),
 C23(H23A,H23B), C31(H31A,H31B), C37(H37A,H37B), C9(H9A,H9B), C10(H10A,H10B),
 C15(H15A,H15B), C32(H32A,H32B), C19(H19A,H19B), C41(H41A,H41B), C11(H11A,H11B),
  C33(H33A,H33B)
4.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C25(H25), C29(H29), C4(H4), C7(H7), C5(H5), C26(H26), C3(H3),
 C6(H6), C27(H27)
4.d X=CH2 refined with riding coordinates:
 C40(H40A,H40B), C18(H18A,H18B)
4.e Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C17(H17A,H17B,H17C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              37265
_shelx_hkl_checksum              30591
_olex2_submission_special_instructions 'No special instructions were received'