A versatile access to vicinal diamine motifs by highly anti-selective asymmetric vinylogous Mannich reactions: an efficient total synthesis of (+)-absouline
Ye, Jian-Liang; Chen, Hang; Zhang, Yu-Feng; Huang, Pei-Qiang; Organic Chemistry Frontiers 3 (2016) 683–; doi:10.1039/C6QO00022C

data_1553420
_publ_section_title
;
 A versatile access to vicinal diamine motifs by highly anti-selective
 asymmetric vinylogous Mannich reactions: an efficient total synthesis of
 (+)-absouline
;
_journal_issue                   6
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              683
_journal_paper_doi               10.1039/C6QO00022C
_journal_volume                  3
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H48 N2 O5 S Si'
_chemical_formula_sum            'C25 H48 N2 O5 S Si'
_chemical_formula_weight         516.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-01-10 deposited with the CCDC.
2016-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.554
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.5809(3)
_cell_length_b                   8.9728(2)
_cell_length_c                   13.3190(3)
_cell_measurement_reflns_used    9510
_cell_measurement_temperature    153(2)
_cell_measurement_theta_max      54.95
_cell_measurement_theta_min      6.13
_cell_volume                     1500.64(6)
_computing_cell_refinement       'Bruker Smart'
_computing_data_collection       'Bruker Smart'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      153(2)
_diffrn_measured_fraction_theta_full 0.9966
_diffrn_measured_fraction_theta_max 0.9951
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0593
_diffrn_reflns_av_unetI/netI     0.0818
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14824
_diffrn_reflns_theta_full        26.0000
_diffrn_reflns_theta_max         27.48
_diffrn_reflns_theta_min         3.06
_exptl_absorpt_coefficient_mu    0.181
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.1437
_exptl_crystal_description       rod
_exptl_crystal_F_000             564.6505
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.9495
_refine_diff_density_min         -1.3965
_refine_diff_density_rms         0.1509
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.03(17)
_refine_ls_d_res_high            0.7702
_refine_ls_d_res_low             6.6467
_refine_ls_goodness_of_fit_ref   0.9634
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    70
_refine_ls_number_parameters     318
_refine_ls_number_reflns         6842
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.9634
_refine_ls_R_factor_all          0.1561
_refine_ls_R_factor_gt           0.0612
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+7.8119P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1222
_refine_ls_wR_factor_ref         0.2001
_reflns_Friedel_coverage         0.992
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              11
_reflns_limit_k_min              -11
_reflns_limit_l_max              17
_reflns_limit_l_min              -17
_reflns_number_gt                3873
_reflns_number_total             6842
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            c6qo00022c2.cif
_cod_data_source_block           a
_cod_depositor_comments
;

2025-06-17
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum          'C2.632 H5.053 N0.211 O0.526 S0.105 Si0.105'
_cod_original_formula_weight         54.40
_cod_original_formula_moiety         '0.11(C25 H48 N2 O5 S Si)'
_cod_original_formula_units_Z            19
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               1553420
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,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:
 C11(H11), C17(H17), C18(H18), C19(H19), C26(H26)
2.b Secondary CH2 refined with riding coordinates:
 C24(H24a,H24b), C29(H29a,H29b)
2.c Aromatic/amide H refined with riding coordinates:
 N8(H8), C10(H10), C14(H14)
2.d Idealised Me refined as rotating group:
 C15(H15a,H15b,H15c), C21(H21a,H21b,H21c), C22(H22a,H22b,H22c), C23(H23a,H23b,
 H23c), C25(H25a,H25b,H25c), C27(H27a,H27b,H27c), C28(H28a,H28b,H28c), C30(H30a,
 H30b,H30c), C31(H31a,H31b,H31c), C32(H32a,H32b,H32c), C33(H33a,H33b,H33c),
 C1(H1a,H1b,H1c)
;
_olex2_submission_special_instructions 'No special instructions were received'