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_1518343
_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         'C33 H28 N2 O4'
_chemical_formula_sum            'C33 H28 N2 O4'
_chemical_formula_weight         516.57
_chemical_name_systematic
;
1,4-dibenzyl-6-(3-oxo-1,3-diphenylpropyl)piperazine-2,3,5-trione
;
_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     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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1648(1)
_cell_length_b                   12.4912(1)
_cell_length_c                   17.1070(2)
_cell_measurement_reflns_used    20167
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.2680
_cell_measurement_theta_min      4.3550
_cell_volume                     2599.46(4)
_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(10)
_diffrn_detector_area_resol_mean 5.1768
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega  -33.00   29.00   1.0000    2.5500
omega____ theta____ kappa____ phi______ frames
    -      -42.5607   38.0000  -60.0000 62

  2 omega -121.00   -8.00   1.0000    2.5500
omega____ theta____ kappa____ phi______ frames
    -      -42.5607  -19.0000  120.0000 113

  3 omega   47.00   99.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -45.0000    0.0000 52

  4 omega   88.00  176.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000   90.0000 88

  5 omega   35.00  138.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -77.0000  -90.0000 103

  6 omega   35.00   68.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000   60.0000 33

  7 omega   36.00   88.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000  -90.0000 52

  8 omega   38.00   64.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -45.0000  -90.0000 26

  9 omega   52.00   83.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000 -180.0000 31

 10 omega -116.00  -11.00   1.0000    2.5500
omega____ theta____ kappa____ phi______ frames
    -      -42.5607  -77.0000  -60.0000 105

 11 omega  -50.00   30.00   1.0000    2.5500
omega____ theta____ kappa____ phi______ frames
    -      -42.5607   38.0000 -120.0000 80

 12 omega   94.00  178.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  125.0000  -60.0000 84

 13 omega   61.00  178.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   15.0000 -120.0000 117

 14 omega   83.00  178.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000  -60.0000 95

 15 omega   79.00  177.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000    0.0000 98

 16 omega -116.00  -11.00   1.0000    2.5500
omega____ theta____ kappa____ phi______ frames
    -      -42.5607  -77.0000   60.0000 105

 17 omega   23.00   98.00   1.0000    2.5500
omega____ theta____ kappa____ phi______ frames
    -       42.5607 -125.0000   90.0000 75

 18 omega   75.00  178.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   77.0000  120.0000 103

 19 omega   35.00  110.00   1.0000   12.2000
omega____ theta____ kappa____ phi______ frames
    -      106.6257 -125.0000  150.0000 75
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0375994000
_diffrn_orient_matrix_UB_12      -0.1158990000
_diffrn_orient_matrix_UB_13      -0.0154317000
_diffrn_orient_matrix_UB_21      0.0938910000
_diffrn_orient_matrix_UB_22      -0.0140012000
_diffrn_orient_matrix_UB_23      -0.0595521000
_diffrn_orient_matrix_UB_31      0.0760940000
_diffrn_orient_matrix_UB_32      -0.0398347000
_diffrn_orient_matrix_UB_33      0.0658184000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0219
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            24936
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.418
_diffrn_reflns_theta_min         4.383
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.700
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93237
_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    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 2221 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         5250
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0243
_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^)+(0.0347P)^2^+0.4172P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0623
_refine_ls_wR_factor_ref         0.0629
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                5145
_reflns_number_total             5250
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc03218g2.cif
_cod_data_source_block           6l
_cod_depositor_comments
'Adding full bibliography for 1518342--1518345.cif.'
_cod_database_code               1518343
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C18 H29 N2 O4'
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H6(0.021) H7(0.021) H8A(0.022) H8B(0.022) H11(0.026) H12(0.029)
 H13(0.029) H14(0.028) H15(0.023) H16A(0.024) H16B(0.024) H18(0.025) H19(0.028)
 H20(0.029) H21(0.031) H22(0.028) H23A(0.027) H23B(0.027) H25(0.028) H26(0.031)
 H27(0.032) H28(0.034) H29(0.03) H31(0.025) H32(0.031) H33(0.033) H34(0.034)
 H35(0.028)
 Fixed X: H6(0.1574) H7(0.1178) H8A(0.3043) H8B(0.2836) H11(0.4382)
 H12(0.6191) H13(0.732) H14(0.6638) H15(0.4817) H16A(0.309) H16B(0.2592)
 H18(0.0883) H19(0.0944) H20(0.2593) H21(0.4168) H22(0.4089) H23A(-0.2395)
 H23B(-0.2077) H25(-0.3882) H26(-0.4653) H27(-0.3708) H28(-0.197) H29(-0.1191)
 H31(0.1897) H32(0.0922) H33(-0.0697) H34(-0.1343) H35(-0.0372)
 Fixed Y: H6(0.467) H7(0.5391) H8A(0.6273) H8B(0.6504) H11(0.3449) H12(0.3462)
 H13(0.4942) H14(0.6425) H15(0.6431) H16A(0.5828) H16B(0.6304) H18(0.4611)
 H19(0.2905) H20(0.1941) H21(0.2671) H22(0.4353) H23A(0.6219) H23B(0.5439)
 H25(0.4599) H26(0.3123) H27(0.2269) H28(0.2888) H29(0.4361) H31(0.79)
 H32(0.9494) H33(0.9494) H34(0.7904) H35(0.6313)
 Fixed Z: H6(0.064) H7(0.1893) H8A(0.1128) H8B(0.2036) H11(0.255) H12(0.301)
 H13(0.2776) H14(0.2098) H15(0.1652) H16A(-0.0035) H16B(-0.0829) H18(-0.1122)
 H19(-0.1676) H20(-0.169) H21(-0.1116) H22(-0.0523) H23A(0.0382) H23B(0.1087)
 H25(0.0696) H26(0.0069) H27(-0.0945) H28(-0.1314) H29(-0.0682) H31(0.0973)
 H32(0.1163) H33(0.1898) H34(0.2452) H35(0.2264)
;
_olex2_submission_special_instructions 'No special instructions were received'