Stereoselective synthesis of (-)-desethyleburnamonine, (-)-vindeburnol and (-)-3-epitacamonine: observation of a substrate dependent diastereoselectivity reversal of an aldol reaction.
Mondal, Pravat; Argade, Narshinha P.; Organic & biomolecular chemistry 14 (2016) 10394–10406; doi:10.1039/c6ob01438k

data_7155290
_publ_section_title
;
 Stereoselective synthesis of (-)-desethyleburnamonine, (-)-vindeburnol
 and (-)-3-epitacamonine: observation of a substrate dependent
 diastereoselectivity reversal of an aldol reaction.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10394
_journal_page_last               10406
_journal_paper_doi               10.1039/c6ob01438k
_journal_volume                  14
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H26 N2 O6 S'
_chemical_formula_sum            'C25 H26 N2 O6 S'
_chemical_formula_weight         482.54
_chemical_name_systematic        'Amide ester'
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-09-12
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled Nov  7 2012 10:34:12, GUI svn.r4372)
;
_audit_update_record
;
2015-09-13 deposited with the CCDC.
2016-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.4819(3)
_cell_length_b                   12.1332(5)
_cell_length_c                   25.2260(8)
_cell_measurement_reflns_used    3638
_cell_measurement_temperature    298
_cell_measurement_theta_max      28.4830
_cell_measurement_theta_min      3.6300
_cell_volume                     2290.00(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      298
_diffrn_detector_area_resol_mean 16.1640
_diffrn_measured_fraction_theta_full 0.9971
_diffrn_measured_fraction_theta_max 0.7319
_diffrn_measurement_details
;
  1 omega   70.00   96.00   1.0000   18.5800
omega____ theta____ kappa____ phi______ frames
    -       19.0920 -178.0000  -30.0000 26

  2 omega  -48.00   40.00   1.0000   18.5800
omega____ theta____ kappa____ phi______ frames
    -       19.0920  -57.0000   30.0000 88

  3 omega   37.00   63.00   1.0000   18.5800
omega____ theta____ kappa____ phi______ frames
    -       19.0920  178.0000 -120.0000 26

  4 omega   61.00   88.00   1.0000   18.5800
omega____ theta____ kappa____ phi______ frames
    -       19.0920   77.0000   90.0000 27
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0493075000
_diffrn_orient_matrix_UB_12      0.0483258000
_diffrn_orient_matrix_UB_13      0.0060552000
_diffrn_orient_matrix_UB_21      -0.0099778000
_diffrn_orient_matrix_UB_22      0.0109850000
_diffrn_orient_matrix_UB_23      -0.0274583000
_diffrn_orient_matrix_UB_31      -0.0803595000
_diffrn_orient_matrix_UB_32      -0.0309937000
_diffrn_orient_matrix_UB_33      -0.0003013000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            7533
_diffrn_reflns_theta_full        29.08
_diffrn_reflns_theta_max         29.08
_diffrn_reflns_theta_min         2.95
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.187
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.958
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.259
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4489
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0447
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0415P)^2^+0.5074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1018
_refine_ls_wR_factor_ref         0.1063
_reflns_number_gt                3825
_reflns_number_total             6141
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6ob01438k2.cif
_cod_data_source_block           pravat01
_cod_depositor_comments
'Adding full bibliography for 7155290--7155292.cif.'
_cod_database_code               7155290
_chemical_oxdiff_formula         'C10 H15 N6 O4 S4'
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H62 of C62, H65 of C65, {H48A,H48B} of C48, {H49A,H49B} of C49, H52 of C52,
  {H54A,H54B} of C54, H55 of C55, H57 of C57, H58 of C58, {H40A,H40B} of C40,
  H38 of C38, {H35A,H35B} of C35, H24 of C24, H43 of C43
 At 1.5 times of:
  {H60A,H60B,H60C} of C60, {H64A,H64B,H64C} of C64, H5 of O5
2.a Riding coordinates:
 O5(H5)
2.b Ternary CH refined with riding coordinates:
 C24(H24)
2.c Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C40(H40A,H40B), C48(H48A,H48B), C49(H49A,H49B), C54(H54A,H54B)
2.d Aromatic/amide H refined with riding coordinates:
 C38(H38), C43(H43), C52(H52), C55(H55), C57(H57), C58(H58), C62(H62), C65(H65)
2.e Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C64(H64A,H64B,H64C)
;