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_1553421
_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         'C20 H27 Cl N2 O4 S, 0.5(H2 O)'
_chemical_formula_sum            'C20 H28 Cl N2 O4.5 S'
_chemical_formula_weight         435.96
_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_Int_Tables_number      19
_audit_creation_date             2016-01-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-01-10 deposited with the CCDC.
2016-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.701(2)
_cell_length_b                   14.628(3)
_cell_length_c                   25.939(5)
_cell_measurement_reflns_used    4645
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      21.34
_cell_measurement_theta_min      2.34
_cell_volume                     4439.8(15)
_computing_cell_refinement       'SAINT v6.28A (Bruker, 2002)'
_computing_data_reduction        'SAINT v6.28A (Bruker, 2002)'
_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    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.9966
_diffrn_measured_fraction_theta_max 0.9082
_diffrn_measurement_device_type  'CCD area detector'
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.1325
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            27913
_diffrn_reflns_theta_full        26.0000
_diffrn_reflns_theta_max         28.81
_diffrn_reflns_theta_min         1.57
_exptl_absorpt_coefficient_mu    0.296
_exptl_absorpt_correction_T_max  1.000000
_exptl_absorpt_correction_T_min  0.692929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS v.2.03 (Bruker,200?) was used for absorption correction.
R(int) was 0.2141 before and 0.0525 after correction.
The Ratio of minimum to maximum transmission is 0.6929.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    1.3043
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1851.0178
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.4833
_refine_diff_density_min         -0.4248
_refine_diff_density_rms         0.0910
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.08(7)
_refine_ls_d_res_high            0.7375
_refine_ls_d_res_low             12.9696
_refine_ls_goodness_of_fit_ref   1.0281
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    85
_refine_ls_number_parameters     534
_refine_ls_number_reflns         10535
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0281
_refine_ls_R_factor_all          0.0930
_refine_ls_R_factor_gt           0.0653
_refine_ls_shift/su_max          0.0000
_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^+1.6986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1515
_refine_ls_wR_factor_ref         0.1711
_reflns_Friedel_coverage         0.870
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              19
_reflns_limit_k_min              -19
_reflns_limit_l_max              35
_reflns_limit_l_min              -34
_reflns_number_gt                7921
_reflns_number_total             10535
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            c6qo00022c2.cif
_cod_data_source_block           y0104m
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-scan' was
changed to 'multi-scan' in accordance with the
/home/saulius/struct/COD-crude-data/automatic-downloads/DataCite-retrospective/RSC/depositions/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 

2025-06-17
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C1.798 H2.517 Cl0.09 N0.18 O0.404 S0.09'
_cod_original_formula_weight         39.19
_cod_original_formula_moiety         '0.09(C20 H27 Cl N2 O4 S), 0.04(H2 O)'
_cod_original_formula_units_Z            89
_cod_original_cell_volume        4440.0(13)
_cod_original_sg_symbol_Hall     ' P 2ac 2ab'
_cod_database_code               1553421
_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, All O(H,H) groups
2.a Free rotating group:
 O2(H2a,H2b)
2.b Ternary CH refined with riding coordinates:
 C8(H8), C19(H19), C46(H46), C55(H55)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C22(H22), C27(H27), C28(H28), C29(H29), C31(H31), C35(H35),
 C37(H37), C40(H40), C44(H44), C50(H50), C53(H53)
2.d Idealised Me refined as rotating group:
 C18(H18a,H18b,H18c), C30(H30a,H30b,H30c), C32(H32a,H32b,H32c), C33(H33a,H33b,
 H33c), C36(H36a,H36b,H36c), C39(H39a,H39b,H39c), C43(H43a,H43b,H43c), C45(H45a,
 H45b,H45c), C47(H47a,H47b,H47c), C51(H51a,H51b,H51c), C57(H57a,H57b,H57c),
 C1(H1a,H1b,H1c)
;
_olex2_submission_special_instructions 'No special instructions were received'