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_7155992
_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         'C17 H19 N O5'
_chemical_formula_sum            'C17 H19 N O5'
_chemical_formula_weight         317.33
_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_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-08-16
_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                 93.7727(16)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.66134(17)
_cell_length_b                   5.45597(10)
_cell_length_c                   14.8724(2)
_cell_measurement_reflns_used    4618
_cell_measurement_temperature    291.84(10)
_cell_measurement_theta_max      72.5220
_cell_measurement_theta_min      5.3070
_cell_volume                     782.25(2)
_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      air
_diffrn_ambient_temperature      291.84(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0769
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
  1 omega  -29.00   49.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -57.0000    0.0000 78

  2 omega   16.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -99.0000  -60.0000 26

  3 omega   45.00   73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -99.0000  -30.0000 28

  4 omega    1.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -99.0000  -30.0000 39

  5 omega  -32.00   50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -38.0000 -150.0000 82

  6 omega   48.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   19.0000 -180.0000 26

  7 omega   90.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 25

  8 omega   92.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -180.0000 84

  9 omega   83.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 10 omega  127.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 46

 11 omega  148.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 25

 12 omega  132.00  171.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 39

 13 omega  127.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 46

 14 omega   99.00  125.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   90.0000 26

 15 omega   92.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 26

 16 omega   90.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  150.0000 26

 17 omega   91.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 27

 18 omega   93.00  119.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 26

 19 omega   90.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   90.0000 26

 20 omega   92.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  120.0000 26

 21 omega   91.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 27

 22 omega   87.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 23 omega   85.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 25

 24 omega   92.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  120.0000 26

 25 omega   79.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   90.0000 28

 26 omega   57.00   92.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  150.0000 35

 27 omega   44.00   70.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000  150.0000 26

 28 omega   44.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 66

 29 omega   39.00   64.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 25

 30 omega   51.00  132.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -120.0000 81

 31 omega   46.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000 -180.0000 62

 32 omega   46.00   81.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 35

 33 omega    8.00   74.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926  -99.0000 -180.0000 66

 34 omega   23.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   57.0000  120.0000 79

 35 omega   53.00  101.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   77.0000  150.0000 48

 36 omega   25.00   50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.8926   77.0000  150.0000 25
;
_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      -0.0715333000
_diffrn_orient_matrix_UB_12      -0.0843178000
_diffrn_orient_matrix_UB_13      -0.0903528000
_diffrn_orient_matrix_UB_21      -0.1328415000
_diffrn_orient_matrix_UB_22      0.1374627000
_diffrn_orient_matrix_UB_23      0.0221899000
_diffrn_orient_matrix_UB_31      0.0527699000
_diffrn_orient_matrix_UB_32      0.2317705000
_diffrn_orient_matrix_UB_33      -0.0460010000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0137
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            5564
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.629
_diffrn_reflns_theta_min         4.587
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.827
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76488
_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    1.347
_exptl_crystal_description       prism
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.141
_refine_diff_density_min         -0.146
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1174 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2925
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0546P)^2^+0.0855P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0899
_refine_ls_wR_factor_ref         0.0904
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    0.922
_reflns_Friedel_fraction_max     0.890
_reflns_number_gt                2875
_reflns_number_total             2925
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02700a2.cif
_cod_data_source_block           fsarein
_cod_depositor_comments
'Adding full bibliography for 7155991--7155993.cif.'
_cod_database_code               7155992
_chemical_oxdiff_formula         'C H N O'
_reflns_odcompleteness_completeness 99.30
_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
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C)
;
_shelx_res_checksum              15055
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'