Highly enantioselective access to diketopiperazines via cinchona alkaloid catalyzed Michael additions
Cabanillas, Alejandro; Davies, Christopher D.; Male, Louise; Simpkins, Nigel S.; Chem. Sci. 6 (2015) 1350–; doi:10.1039/C4SC03218G

data_1518345
_publ_section_title
;
 Highly enantioselective access to diketopiperazines via cinchona alkaloid
 catalyzed Michael additions
;
_journal_issue                   2
_journal_name_full               'Chem. Sci.'
_journal_page_first              1350
_journal_paper_doi               10.1039/C4SC03218G
_journal_volume                  6
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H22 N2 O5'
_chemical_formula_sum            'C22 H22 N2 O5'
_chemical_formula_weight         394.41
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-01
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2014-08-01 deposited with the CCDC.
2014-11-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.5659(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.14306(17)
_cell_length_b                   6.28576(7)
_cell_length_c                   13.0165(2)
_cell_measurement_reflns_used    9699
_cell_measurement_temperature    100.01(13)
_cell_measurement_theta_max      74.2230
_cell_measurement_theta_min      3.8150
_cell_volume                     941.82(2)
_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    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01(13)
_diffrn_detector_area_resol_mean 5.1768
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega  -48.00  -22.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -      -42.8107   38.0000   30.0000 26

  2 omega -113.00  -19.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -      -42.8107  -57.0000    0.0000 94

  3 omega   -8.00   22.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -      -42.8107   38.0000   30.0000 30

  4 omega   10.00   37.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -       42.8107  -99.0000 -120.0000 27

  5 omega   47.00   78.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -       42.8107  -99.0000 -120.0000 31

  6 omega -116.00  -90.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -94.0000    0.0000 26

  7 omega  -89.00    8.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      -43.5000   15.0000    0.0000 97

  8 omega -121.00  -91.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -94.0000 -120.0000 30

  9 omega   11.00   36.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      -43.5000   15.0000    0.0000 25

 10 omega   88.00  178.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000  150.0000 90

 11 omega   33.00   85.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000 -150.0000 52

 12 omega   49.00  102.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000  150.0000 53

 13 omega   41.00   85.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -45.0000  120.0000 44

 14 omega   94.00  173.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  125.0000    0.0000 79

 15 omega   41.00   78.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000   60.0000 37

 16 omega   56.00   86.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000 -120.0000 30

 17 omega   73.00  108.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000   30.0000 35

 18 omega   36.00   79.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000    0.0000 43

 19 omega   28.00   54.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000   30.0000 26

 20 omega   47.00  119.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -61.0000    0.0000 72

 21 omega   94.00  178.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   45.0000 -150.0000 84

 22 omega   55.00   90.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257 -125.0000  -30.0000 35

 23 omega -113.00  -16.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -      -42.8107  -57.0000 -120.0000 97

 24 omega  -45.00  -16.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -      -42.8107  -57.0000  120.0000 29

 25 omega -117.00  -96.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -      -42.8107  -77.0000   90.0000 21

 26 omega    1.00   83.00   1.0000   14.9200
omega____ theta____ kappa____ phi______ frames
    -       42.8107  -99.0000  120.0000 82

 27 omega  -43.00  -12.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -77.0000 -150.0000 31

 28 omega -114.00  -16.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -61.0000  -60.0000 98

 29 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000 -120.0000 98

 30 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  -90.0000 98

 31 omega   83.00  178.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000   60.0000 95

 32 omega   25.00   92.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000 -120.0000 67

 33 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000   90.0000 98

 34 omega   83.00  178.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000  -30.0000 95

 35 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000    0.0000 98

 36 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  -30.0000 98

 37 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000   60.0000 98

 38 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  150.0000 98

 39 omega   35.00  111.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257 -125.0000  120.0000 76

 40 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  120.0000 98

 41 omega   79.00  177.00   1.0000   59.6600
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000 -180.0000 98
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0618077000
_diffrn_orient_matrix_UB_12      -0.2166674000
_diffrn_orient_matrix_UB_13      0.0265118000
_diffrn_orient_matrix_UB_21      0.0933511000
_diffrn_orient_matrix_UB_22      0.0770290000
_diffrn_orient_matrix_UB_23      -0.0484890000
_diffrn_orient_matrix_UB_31      0.0733380000
_diffrn_orient_matrix_UB_32      0.0846313000
_diffrn_orient_matrix_UB_33      0.1119899000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            16277
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.439
_diffrn_reflns_theta_min         3.582
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.819
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65159
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       needle
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.4089
_exptl_crystal_size_mid          0.0355
_exptl_crystal_size_min          0.0295
_refine_diff_density_max         0.191
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1568 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     267
_refine_ls_number_reflns         3748
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0304
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0387P)^2^+0.1322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0690
_refine_ls_wR_factor_ref         0.0706
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.967
_reflns_number_gt                3593
_reflns_number_total             3748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc03218g2.cif
_cod_data_source_block           11d
_cod_depositor_comments
'Adding full bibliography for 1518342--1518345.cif.'
_cod_database_code               1518345
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C22 H22 N2 O5'
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.731
_reflns_odcompleteness_completeness 99.62
_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:
 C5(H5), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C12(H12A,H12B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22),
 C23(H23), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'