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_1518342
_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 H27 Br N2 O4'
_chemical_formula_sum            'C33 H27 Br N2 O4'
_chemical_formula_weight         595.47
_chemical_name_systematic
;
1,4-dibenzyl-6-(3-(2-bromophenyl)-3-oxo-1-phenylpropyl)piperazine-2,3,5-trione
;
_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             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                 106.7030(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.71430(10)
_cell_length_b                   22.59340(10)
_cell_length_c                   12.66410(10)
_cell_measurement_reflns_used    45015
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.3680
_cell_measurement_theta_min      3.6110
_cell_volume                     2662.23(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 0.994
_diffrn_measurement_details
;
  1 omega   32.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.5607 -125.0000   90.0000 59

  2 omega -124.00   40.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000    0.0000  150.0000 164

  3 omega  -48.00   11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000   30.0000 -150.0000 59

  4 omega  -91.00  -33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -45.0000  -30.0000 58

  5 omega -119.00  -90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -94.0000   30.0000 29

  6 omega   37.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -61.0000  150.0000 97

  7 omega   36.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -45.0000    0.0000 53

  8 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000  -90.0000 95

  9 omega  123.00  177.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  -60.0000 54

 10 omega   83.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  -60.0000 26

 11 omega   74.00  100.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000 -120.0000 26

 12 omega   80.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  -30.0000 37

 13 omega   90.00  122.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257 -125.0000 -180.0000 32

 14 omega   49.00   86.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -30.0000    0.0000 37

 15 omega   46.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257 -125.0000 -180.0000 36

 16 omega   32.00   93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000  120.0000 61

 17 omega   25.00   51.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000 -120.0000 26

 18 omega  149.00  176.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   61.0000  -30.0000 27

 19 omega   63.00  134.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   15.0000   60.0000 71

 20 omega   96.00  160.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  125.0000  120.0000 64

 21 omega   84.00  111.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   45.0000  -30.0000 27

 22 omega   37.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000   30.0000 65

 23 omega -115.00  -20.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5607  -38.0000   60.0000 95

 24 omega -114.00  -16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -61.0000 -180.0000 98

 25 omega  -71.00   27.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000   61.0000  -90.0000 98

 26 omega -114.00  -16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -61.0000  -90.0000 98

 27 omega -117.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -77.0000  150.0000 105

 28 omega -117.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -77.0000   60.0000 105

 29 omega   25.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000  120.0000 84

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

 31 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   30.0000 -180.0000 95

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

 33 omega   75.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   77.0000  -90.0000 103

 34 omega   75.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   77.0000  -30.0000 103

 35 omega   25.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257  -94.0000  -30.0000 84

 36 omega   75.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   77.0000 -180.0000 103

 37 omega   75.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   77.0000  150.0000 103

 38 omega   75.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   77.0000 -150.0000 103

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

 40 omega   83.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6257   45.0000   90.0000 95
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0963482000
_diffrn_orient_matrix_UB_12      0.0497721000
_diffrn_orient_matrix_UB_13      -0.0648837000
_diffrn_orient_matrix_UB_21      -0.1206808000
_diffrn_orient_matrix_UB_22      -0.0185981000
_diffrn_orient_matrix_UB_23      0.0497629000
_diffrn_orient_matrix_UB_31      0.0596187000
_diffrn_orient_matrix_UB_32      0.0427540000
_diffrn_orient_matrix_UB_33      0.0971865000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            50958
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.525
_diffrn_reflns_theta_min         3.644
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.456
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78853
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.299
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.277
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 5089 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.027(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     721
_refine_ls_number_reflns         10745
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0187
_refine_ls_R_factor_gt           0.0185
_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^)+(0.0259P)^2^+0.8278P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0475
_refine_ls_wR_factor_ref         0.0477
_reflns_Friedel_coverage         0.935
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                10661
_reflns_number_total             10745
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc03218g2.cif
_cod_data_source_block           6m
_cod_depositor_comments
'Adding full bibliography for 1518342--1518345.cif.'
_cod_database_code               1518342
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C33 H27 Br N2 O4'
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.527
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H6(0.014) H7(0.015) H8A(0.017) H8B(0.017) H12(0.021) H13(0.022)
 H14(0.021) H15(0.02) H16A(0.018) H16B(0.018) H18(0.02) H19(0.025) H20(0.027)
 H21(0.027) H22(0.022) H23A(0.019) H23B(0.019) H25(0.022) H26(0.027) H27(0.03)
 H28(0.03) H29(0.023) H31(0.019) H32(0.021) H33(0.022) H34(0.025) H35(0.02)
 H106(0.016) H107(0.017) H10A(0.017) H10B(0.017) H112(0.024) H113(0.03)
 H114(0.03) H115(0.025) H11A(0.021) H11B(0.021) H118(0.024) H119(0.029)
 H120(0.029) H121(0.031) H122(0.024) H12A(0.02) H12B(0.02) H125(0.025)
 H126(0.03) H127(0.029) H128(0.025) H129(0.021) H131(0.019) H132(0.022)
 H133(0.024) H134(0.024) H135(0.019)
 Fixed X: H6(0.6454) H7(0.4456) H8A(0.545) H8B(0.3856) H12(0.812) H13(0.7364)
 H14(0.578) H15(0.4972) H16A(0.4792) H16B(0.5973) H18(0.8619) H19(1.0069)
 H20(0.9077) H21(0.6639) H22(0.5175) H23A(0.8088) H23B(0.8564) H25(1.0561)
 H26(1.2926) H27(1.3773) H28(1.2237) H29(0.9886) H31(0.4341) H32(0.2717)
 H33(0.0939) H34(0.0772) H35(0.2452) H106(0.1469) H107(0.1764) H10A(-0.0197)
 H10B(-0.1252) H112(-0.4937) H113(-0.5433) H114(-0.3696) H115(-0.1496) H11A(-
 0.1429) H11B(-0.1569) H118(-0.0886) H119(0.0311) H120(0.1886) H121(0.2213)
 H122(0.0983) H12A(0.4772) H12B(0.388) H125(0.5746) H126(0.6374) H127(0.5351)
 H128(0.3669) H129(0.3029) H131(-0.144) H132(-0.171) H133(0.0247) H134(0.2472)
 H135(0.2743)
 Fixed Y: H6(0.4035) H7(0.4995) H8A(0.4485) H8B(0.4748) H12(0.6356)
 H13(0.5725) H14(0.4949) H15(0.4804) H16A(0.35) H16B(0.353) H18(0.3634)
 H19(0.2943) H20(0.206) H21(0.1859) H22(0.2556) H23A(0.6127) H23B(0.5851)
 H25(0.4998) H26(0.4898) H27(0.55) H28(0.6189) H29(0.6299) H31(0.355)
 H32(0.2801) H33(0.2969) H34(0.3896) H35(0.4634) H106(0.3953) H107(0.2928)
 H10A(0.3386) H10B(0.3154) H112(0.2678) H113(0.167) H114(0.1043) H115(0.1425)
 H11A(0.4142) H11B(0.4617) H118(0.4607) H119(0.5321) H120(0.5986) H121(0.5953)
 H122(0.5254) H12A(0.3918) H12B(0.4032) H125(0.2959) H126(0.2016) H127(0.165)
 H128(0.222) H129(0.3155) H131(0.2876) H132(0.2263) H133(0.1719) H134(0.1779)
 H135(0.2382)
 Fixed Z: H6(0.5853) H7(0.5799) H8A(0.4091) H8B(0.3771) H12(0.2291) H13(0.077)
 H14(0.0796) H15(0.2338) H16A(0.7132) H16B(0.8309) H18(0.7629) H19(0.7073)
 H20(0.6223) H21(0.5954) H22(0.6476) H23A(0.7418) H23B(0.6412) H25(0.7051)
 H26(0.817) H27(0.9722) H28(1.0179) H29(0.9045) H31(0.4536) H32(0.4609)
 H33(0.5495) H34(0.6277) H35(0.6259) H106(0.2573) H107(0.266) H10A(0.3175)
 H10B(0.2034) H112(0.3726) H113(0.3413) H114(0.3068) H115(0.3004) H11A(0.1842)
 H11B(0.0876) H118(0.3578) H119(0.4851) H120(0.4389) H121(0.2624) H122(0.1341)
 H12A(0.0746) H12B(-0.051) H125(0.1325) H126(0.0849) H127(-0.0927) H128(-
 0.2224) H129(-0.1753) H131(0.035) H132(-0.1185) H133(-0.1387) H134(-0.0047)
 H135(0.1501)
;
_olex2_submission_special_instructions 'No special instructions were received'