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_7155993
_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                   6.38939(11)
_cell_length_b                   7.59037(13)
_cell_length_c                   26.8562(5)
_cell_measurement_reflns_used    6362
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.6180
_cell_measurement_theta_min      5.9900
_cell_volume                     1302.47(4)
_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      100(2)
_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 0.997
_diffrn_measurement_details
;
  1 omega  -17.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -38.0000  -60.0000 70

  2 omega   63.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   19.0000 -120.0000 26

  3 omega    2.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -99.0000 -180.0000 56

  4 omega   45.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926 -125.0000  -60.0000 37

  5 omega   43.00   79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926 -125.0000   60.0000 36

  6 omega   60.00   85.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   90.0000 25

  7 omega   53.00  112.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   60.0000 59

  8 omega   48.00   86.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 38

  9 omega   41.00  119.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000   30.0000 78

 10 omega   93.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000    0.0000 83

 11 omega  143.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000    0.0000 34

 12 omega  113.00  148.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000   30.0000 35

 13 omega   82.00  149.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  -60.0000 67

 14 omega  108.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -150.0000 26

 15 omega   61.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000   30.0000 50

 16 omega  -26.00   62.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -19.0000 -150.0000 88

 17 omega   44.00   79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 35

 18 omega   44.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 31

 19 omega   46.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 43

 20 omega   46.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000  -30.0000 56

 21 omega   47.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000   60.0000 63

 22 omega   41.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 37

 23 omega   39.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 52

 24 omega  -29.00   49.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -57.0000   60.0000 78

 25 omega  -28.00   38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -57.0000 -180.0000 66
;
_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      0.0141163000
_diffrn_orient_matrix_UB_12      -0.1781790000
_diffrn_orient_matrix_UB_13      -0.0272792000
_diffrn_orient_matrix_UB_21      0.0127056000
_diffrn_orient_matrix_UB_22      -0.0960467000
_diffrn_orient_matrix_UB_23      0.0504337000
_diffrn_orient_matrix_UB_31      -0.2403615000
_diffrn_orient_matrix_UB_32      -0.0155515000
_diffrn_orient_matrix_UB_33      0.0011160000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            8224
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.734
_diffrn_reflns_theta_min         6.059
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.817
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84682
_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    1.343
_exptl_crystal_description       prism
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.180
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 998 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         2564
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0308
_refine_ls_R_factor_gt           0.0304
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0415P)^2^+0.2133P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0780
_refine_ls_wR_factor_ref         0.0785
_reflns_Friedel_coverage         0.671
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                2525
_reflns_number_total             2564
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02700a2.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 7155991--7155993.cif.'
_cod_database_code               7155993
_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              52153
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'