The direct and highly diastereoselective synthesis of 3,4-epoxy-2-piperidones. Application to the total synthesis and absolute configurational assignment of 3α,4α-epoxy-5β-pipermethystine.
Osorio-Nieto, Urbano; Vázquez-Amaya, Laura Y; Höpfl, Herbert; Quintero, Leticia; Sartillo-Piscil, Fernando; Organic & biomolecular chemistry 16 (2017) 77–88; doi:10.1039/c7ob02700a

data_7155991
_publ_section_title
;
 The direct and highly diastereoselective synthesis of
 3,4-epoxy-2-piperidones. Application to the total synthesis and absolute
 configurational assignment of 3\a,4\a-epoxy-5\b-pipermethystine.
;
_journal_issue                   1
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              77
_journal_page_last               88
_journal_paper_doi               10.1039/c7ob02700a
_journal_volume                  16
_journal_year                    2017
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C14 H17 N O4'
_chemical_formula_sum            'C14 H17 N O4'
_chemical_formula_weight         263.28
_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     dual
_audit_creation_date             2017-02-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2017-09-27 deposited with the CCDC.
2017-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.32903(9)
_cell_length_b                   8.54815(13)
_cell_length_c                   23.7167(4)
_cell_measurement_reflns_used    3176
_cell_measurement_temperature    99.97(12)
_cell_measurement_theta_max      72.5060
_cell_measurement_theta_min      5.4760
_cell_volume                     1283.11(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0769
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_details
;
  1 omega  -30.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -38.0000   30.0000 84

  2 omega   24.00   50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   38.0000   90.0000 26

  3 omega   56.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926 -125.0000  150.0000 28

  4 omega   49.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000  150.0000 55

  5 omega   42.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   30.0000 28

  6 omega   53.00   84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 31

  7 omega   46.00   97.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000 -120.0000 51

  8 omega   39.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 50

  9 omega   42.00   92.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 50

 10 omega   72.00   99.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   57.0000  -60.0000 27

 11 omega  100.00  138.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   30.0000 38

 12 omega  140.00  175.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   30.0000 35

 13 omega  115.00  141.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 26

 14 omega   97.00  165.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -150.0000 68

 15 omega  -25.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -77.0000  -30.0000 83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0069442000
_diffrn_orient_matrix_UB_12      -0.0734357000
_diffrn_orient_matrix_UB_13      0.0592684000
_diffrn_orient_matrix_UB_21      0.0130026000
_diffrn_orient_matrix_UB_22      0.1643666000
_diffrn_orient_matrix_UB_23      0.0264170000
_diffrn_orient_matrix_UB_31      -0.2430368000
_diffrn_orient_matrix_UB_32      0.0066833000
_diffrn_orient_matrix_UB_33      0.0031065000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0208
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            4408
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.706
_diffrn_reflns_theta_min         3.727
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90507
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.363
_exptl_crystal_description       prism
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.174
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 952 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.21(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         2480
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0297
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0361P)^2^+0.2771P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0743
_reflns_Friedel_coverage         0.678
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                2408
_reflns_number_total             2480
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02700a2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7155991--7155993.cif.'
_cod_database_code               7155991
_chemical_oxdiff_formula         'C H N O'
_reflns_odcompleteness_completeness 99.86
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3A)
;
_shelx_res_checksum              33346
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'