Asymmetric Synthesis of 2-Substituted Azetidin-3-ones via Metalated SAMP/RAMP Hydrazones.
Pancholi, Alpa K.; Geden, Joanna V.; Clarkson, Guy J.; Shipman, Michael; The Journal of organic chemistry 81 (2016) 7984–7992; doi:10.1021/acs.joc.6b01284

data_4037022
_publ_section_title
;
 Asymmetric Synthesis of 2-Substituted Azetidin-3-ones via Metalated
 SAMP/RAMP Hydrazones.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7984
_journal_page_last               7992
_journal_paper_doi               10.1021/acs.joc.6b01284
_journal_volume                  81
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H32 N4 O4'
_chemical_formula_sum            'C23 H32 N4 O4'
_chemical_formula_weight         428.52
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.24482(4)
_cell_length_b                   13.77957(5)
_cell_length_c                   18.20928(9)
_cell_measurement_reflns_used    74988
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.5390
_cell_measurement_theta_min      3.9880
_cell_volume                     2319.674(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -118.00  -9.00   1.00    3.00    --  -41.82 -77.00 -90.00  109
  2  \w    -70.00  31.00   1.00    3.00    --  -41.82  57.00  30.00  101
  3  \w    -33.00  66.00   1.00    3.00    --   41.82 -37.00  90.00   99
  4  \w     18.00  94.00   1.00    3.00    --   41.82-119.00 127.00   76
  5  \w     74.00 167.00   1.00   12.00    --  107.00 156.00   8.00   93
  6  \w     24.00 109.00   1.00   12.00    --  107.00 -94.00 120.00   85
  7  \w     34.00 121.00   1.00   12.00    --  107.00-125.00-150.00   87
  8  \w     94.00 178.00   1.00   12.00    --  107.00 125.00 -60.00   84
  9  \w     94.00 178.00   1.00   12.00    --  107.00 125.00 -30.00   84
 10  \w     34.00 121.00   1.00   12.00    --  107.00-125.00 -30.00   87
 11  \w     24.00 109.00   1.00   12.00    --  107.00 -94.00 150.00   85
 12  \w     94.00 178.00   1.00   12.00    --  107.00 125.00 120.00   84
 13  \w     34.00 121.00   1.00   12.00    --  107.00-125.00  60.00   87
 14  \w     79.00 178.00   1.00   12.00    --  107.00  30.00-120.00   99
 15  \w     24.00 109.00   1.00   12.00    --  107.00 -94.00 -30.00   85
 16  \w     24.00 109.00   1.00   12.00    --  107.00 -94.00  90.00   85
 17  \w     35.00 136.00   1.00   12.00    --  107.00 -61.00-180.00  101
 18  \w     34.00 121.00   1.00   12.00    --  107.00-125.00  90.00   87
 19  \w     81.00 178.00   1.00   12.00    --  107.00  45.00  60.00   97
 20  \w     34.00 133.00   1.00   12.00    --  107.00 -45.00-150.00   99
 21  \w     78.00 178.00   1.00   12.00    --  107.00  61.00   0.00  100
 22  \w     34.00 121.00   1.00   12.00    --  107.00-125.00-120.00   87
 23  \w     54.00 178.00   1.00   12.00    --  107.00  15.00-150.00  124
 24  \w     34.00 133.00   1.00   12.00    --  107.00 -45.00   0.00   99
 25  \w     81.00 178.00   1.00   12.00    --  107.00  45.00  30.00   97
 26  \w     33.00 132.00   1.00   12.00    --  107.00 -38.00  74.43   99
 27  \w   -118.00  -9.00   1.00    3.00    --  -41.82 -77.00  30.00  109
 28  \w   -118.00  -9.00   1.00    3.00    --  -41.82 -77.00 120.00  109
 29  \w   -114.00 -14.00   1.00    3.00    --  -41.82 -57.00 -30.00  100
 30  \w   -118.00  -9.00   1.00    3.00    --  -41.82 -77.00  90.00  109
 31  \w   -114.00 -14.00   1.00    3.00    --  -41.82 -57.00 150.00  100
 32  \w     40.00 119.00   1.00    3.00    --   41.82-156.00 -27.00   79
 33  \w     81.00 178.00   1.00   12.00    --  107.00  45.00 -60.00   97
 34  \w     78.00 178.00   1.00   12.00    --  107.00  61.00-180.00  100
 35  \w     74.00 178.00   1.00   12.00    --  107.00  77.00  60.00  104
 36  \w     74.00 178.00   1.00   12.00    --  107.00  77.00 150.00  104
 37  \w     78.00 178.00   1.00   12.00    --  107.00  61.00 120.00  100
 38  \w     74.00 178.00   1.00   12.00    --  107.00  77.00 120.00  104
 39  \w     74.00 178.00   1.00   12.00    --  107.00  77.00-150.00  104
 40  \w     78.00 178.00   1.00   12.00    --  107.00  61.00 -60.00  100
 41  \w     74.00 178.00   1.00   12.00    --  107.00  77.00 -60.00  104
 42  \w     78.00 178.00   1.00   12.00    --  107.00  61.00 -30.00  100
 43  \w     78.00 178.00   1.00   12.00    --  107.00  61.00  60.00  100
 44  \w     78.00 178.00   1.00   12.00    --  107.00  61.00 -90.00  100
 45  \w     74.00 178.00   1.00   12.00    --  107.00  77.00-120.00  104
 46  \w     74.00 178.00   1.00   12.00    --  107.00  77.00 -30.00  104
 47  \w     78.00 178.00   1.00   12.00    --  107.00  61.00-120.00  100
 48  \w     78.00 178.00   1.00   12.00    --  107.00  61.00  90.00  100
 49  \w     78.00 178.00   1.00   12.00    --  107.00  61.00  30.00  100
 50  \w     74.00 178.00   1.00   12.00    --  107.00  77.00-180.00  104
 51  \w     78.00 178.00   1.00   12.00    --  107.00  61.00-150.00  100
 52  \w     74.00 178.00   1.00   12.00    --  107.00  77.00 -90.00  104
 53  \w     78.00 178.00   1.00   12.00    --  107.00  61.00 150.00  100
 54  \w     74.00 178.00   1.00   12.00    --  107.00  77.00   0.00  104
 55  \w     74.00 178.00   1.00   12.00    --  107.00  77.00  30.00  104
 56  \w     74.00 178.00   1.00   12.00    --  107.00  77.00  90.00  104
 57  \w   -114.00 -14.00   1.00    3.00    --  -41.82 -57.00 120.00  100
 58  \w   -118.00  -9.00   1.00    3.00    --  -41.82 -77.00-180.00  109
 59  \w   -118.00  -9.00   1.00    3.00    --  -41.82 -77.00 -30.00  109
 60  \w   -114.00 -14.00   1.00    3.00    --  -41.82 -57.00 -90.00  100
 61  \w     23.00  98.00   1.00    3.00    --   41.82-125.00-120.00   75
 62  \w     17.00 116.00   1.00    3.00    --   41.82  37.00  30.00   99
 63  \w     94.00 178.00   1.00   12.00    --  107.00 125.00  60.00   84
 64  \w     81.00 178.00   1.00   12.00    --  107.00  45.00 120.00   97
 65  \w     81.00 178.00   1.00   12.00    --  107.00  45.00-180.00   97
 66  \w     34.00 121.00   1.00   12.00    --  107.00-125.00   0.00   87
 67  \w     78.00 178.00   1.00   12.00    --  107.00  61.00-137.54  100
 68  \w     81.00 178.00   1.00   12.00    --  107.00  45.00   0.00   97
 69  \w     81.00 178.00   1.00   12.00    --  107.00  45.00 150.00   97
 70  \w     25.00 160.00   1.00   12.00    --  107.00 -15.00  90.00  135
 71  \w     81.00 178.00   1.00   12.00    --  107.00  45.00-150.00   97
 72  \w     31.00 140.00   1.00   12.00    --  107.00 -77.00 -30.00  109
 73  \w     81.00 167.00   1.00   12.00    --  107.00  45.00 -30.00   86
 74  \w     35.00 136.00   1.00   12.00    --  107.00 -61.00 -30.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0205220000
_diffrn_orient_matrix_UB_12      0.1093086000
_diffrn_orient_matrix_UB_13      0.0143936000
_diffrn_orient_matrix_UB_21      0.1589266000
_diffrn_orient_matrix_UB_22      -0.0183356000
_diffrn_orient_matrix_UB_23      0.0213253000
_diffrn_orient_matrix_UB_31      0.0457345000
_diffrn_orient_matrix_UB_32      0.0146042000
_diffrn_orient_matrix_UB_33      -0.0805993000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0497
_diffrn_reflns_av_unetI/netI     0.0129
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            108912
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.724
_diffrn_reflns_theta_min         4.023
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.689
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41111
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.227
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.172
_refine_diff_density_min         -0.173
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1987 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4697
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0283
_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^)+(0.0379P)^2^+0.5480P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0723
_refine_ls_wR_factor_ref         0.0727
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4644
_reflns_number_total             4697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01284_si_001.cif
_cod_data_source_block           jg7
_cod_original_cell_volume        2319.672(17)
_cod_database_code               4037022
_chemical_oxdiff_formula         'C23 H32 N4 O4'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H27 of N27, H2 of N2, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H12 of N12, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C4(H4), C5(H5), C6(H6), C7(H7), N27(H27)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C)
2.e Idealised tetrahedral OH refined as rotating group:
 O17(H17)
;
_shelx_res_checksum              24601
_shelx_hkl_checksum              16085
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.968
_oxdiff_exptl_absorpt_empirical_full_min 0.687