Recyclable Organocatalyst-promoted One-pot Michael/aza-Henry/lactamization Reactions for Fluorinated 2-Piperidinones Bearing Four Stereogenic Centres
Huang, Xin; Pham, Kenny; Zhang, Xiaofeng; Yi, Wen-bin; Hyatt, Jeremy; Tran, Anthony P.; Jasinski, Jerry P.; Zhang, Wei; RSC Adv.  (2015) –; doi:10.1039/C5RA15306A

data_7221811
_publ_section_title
;
 Recyclable Organocatalyst-promoted One-pot
 Michael/aza-Henry/lactamization Reactions for Fluorinated 2-Piperidinones
 Bearing Four Stereogenic Centres
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C5RA15306A
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C20 H18 Br F N2 O5'
_chemical_formula_sum            'C20 H18 Br F N2 O5'
_chemical_formula_weight         465.27
_chemical_name_systematic
'6-(4-Bromo-phenyl)-3-fluoro-5-nitro-2-oxo-4-phenyl-piperidine-3-carboxylic acid ethyl ester'
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-16
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_audit_update_record
;
2015-01-11 deposited with the CCDC.
2015-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 131.075(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.744(3)
_cell_length_b                   7.5503(4)
_cell_length_c                   16.0634(18)
_cell_measurement_reflns_used    2133
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      71.3550
_cell_measurement_theta_min      3.6460
_cell_volume                     2079.5(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0416
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega  -63.00  -37.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   90.0000 26

  2 omega -101.00  -66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   90.0000 35

  3 omega  -95.00  -18.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000  -60.0000 77

  4 omega   43.00   72.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.2322  -99.0000 -180.0000 29

  5 omega   39.00   86.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 47

  6 omega   59.00   87.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 28

  7 omega   46.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 25

  8 omega   44.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 39

  9 omega   91.00  172.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -150.0000 81

 10 omega  100.00  164.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 64

 11 omega   57.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.2322  178.0000   30.0000 25

 12 omega  -67.00  -42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000  120.0000 25

 13 omega -106.00  -79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000  120.0000 27

 14 omega   54.00   88.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  150.0000 34

 15 omega   79.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 26

 16 omega   74.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 29

 17 omega   51.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -60.0000 58

 18 omega   40.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 58

 19 omega   53.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       35.2322 -178.0000  150.0000 54

 20 omega  -77.00  -47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000 -178.0000  -60.0000 30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0120175000
_diffrn_orient_matrix_UB_12      -0.2007431000
_diffrn_orient_matrix_UB_13      0.0001951000
_diffrn_orient_matrix_UB_21      -0.0663629000
_diffrn_orient_matrix_UB_22      0.0038838000
_diffrn_orient_matrix_UB_23      -0.1263617000
_diffrn_orient_matrix_UB_31      0.0593791000
_diffrn_orient_matrix_UB_32      -0.0363985000
_diffrn_orient_matrix_UB_33      -0.0146833000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0544
_diffrn_reflns_av_unetI/netI     0.0603
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            3936
_diffrn_reflns_point_group_measured_fraction_full 0.758
_diffrn_reflns_point_group_measured_fraction_max 0.738
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.104
_diffrn_reflns_theta_min         3.650
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.073
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39761
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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    1.486
_exptl_crystal_description       prism
_exptl_crystal_F_000             944
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane and hexanes'
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.658
_refine_diff_density_min         -0.543
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_coef       0.0023(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         2972
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0828P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1306
_refine_ls_wR_factor_ref         0.1329
_reflns_Friedel_coverage         0.384
_reflns_Friedel_fraction_full    0.474
_reflns_Friedel_fraction_max     0.445
_reflns_number_gt                2872
_reflns_number_total             2972
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ra15306a2.cif
_cod_data_source_block           wei-xin-5
_cod_original_cell_volume        2079.5(6)
_cod_database_code               7221811
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C20 H18 F N2 O5 Br'
_chemical_oxdiff_usercomment     'Wei's Wei-Xin-5'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C8(H8), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              82626