Enantioselective Deprotonative Ring Contraction of N1-Methyl-N4-Boc-benzo[e][1,4]diazepine-2,5-diones.
Antolak, Stephanie A.; Yao, Zhong-Ke; Richoux, Gary M.; Slebodnick, Carla; Carlier, Paul R.; Organic letters 16 (2014) 5204–5207; doi:10.1021/ol502586n

data_1517818
_publ_section_title
;
 Enantioselective Deprotonative Ring Contraction of
 N1-Methyl-N4-Boc-benzo[e][1,4]diazepine-2,5-diones.
;
_journal_issue                   19
_journal_name_full               'Organic letters'
_journal_page_first              5204
_journal_page_last               5207
_journal_paper_doi               10.1021/ol502586n
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H30 N2 O6'
_chemical_formula_sum            'C22 H30 N2 O6'
_chemical_formula_weight         418.48
_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             2014-08-18
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.05087(7)
_cell_length_b                   13.52501(11)
_cell_length_c                   18.54998(14)
_cell_measurement_reflns_used    22069
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      75.6752
_cell_measurement_theta_min      3.2649
_cell_volume                     2270.76(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_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(1)
_diffrn_detector_area_resol_mean 8.3174
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega  -67.00   24.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -44.4841   37.0000   60.0000 91

  2 omega -110.00  -45.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -44.4841  -57.0000    0.0000 65

  3 omega  -81.00  -20.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -44.4841  -57.0000   60.0000 61

  4 omega -114.00  -44.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -44.4841  -37.0000 -120.0000 70

  5 omega   15.00   41.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   77.0000   90.0000 26

  6 omega   89.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   77.0000   90.0000 26

  7 omega  -86.00  -60.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -77.0000   60.0000 26

  8 omega  -88.00  -62.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -69.0000   64.0000 26

  9 omega  -86.00  -60.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -77.0000   90.0000 26

 10 omega  -88.00  -63.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -65.0000    5.0000 25

 11 omega  -88.00  -62.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -69.0000   31.0000 26

 12 omega -109.00  -67.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -61.0000   30.0000 42

 13 omega  -92.00  -67.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -61.0000   90.0000 25

 14 omega  -87.00  -62.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -70.0000   20.0000 25

 15 omega  -99.00  -61.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -90.0000  -77.0000    0.0000 38

 16 omega   35.00   68.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000   90.0000 33

 17 omega   59.00  121.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000  150.0000 62

 18 omega   48.00   74.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000 -120.0000 26

 19 omega  115.00  152.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000  -30.0000 37

 20 omega  124.00  176.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000   30.0000 52

 21 omega   77.00  102.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000   30.0000 25

 22 omega   51.00   76.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000   30.0000 25

 23 omega   99.00  167.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   45.0000  150.0000 68

 24 omega   82.00  107.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000    0.0000 25

 25 omega   78.00  105.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000   60.0000 27

 26 omega  118.00  169.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000   60.0000 51

 27 omega   99.00  137.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -77.0000 -180.0000 38

 28 omega   75.00  113.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000 -120.0000 38

 29 omega   80.00  165.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000   90.0000 85

 30 omega   43.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000 -180.0000 26

 31 omega   40.00   66.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -77.0000 -180.0000 26

 32 omega  151.00  177.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000  150.0000 26

 33 omega   35.00   63.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -34.0000  -33.0000 28

 34 omega   85.00  134.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000   30.0000 49

 35 omega   82.00  160.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000    0.0000 78

 36 omega   35.00   67.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000   60.0000 32

 37 omega   66.00   91.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000  -90.0000 25

 38 omega   36.00   61.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000 -120.0000 25

 39 omega   90.00  119.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000   30.0000 29

 40 omega   82.00  133.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000   60.0000 51

 41 omega  100.00  132.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   30.0000  -30.0000 32

 42 omega  153.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   30.0000  -30.0000 25

 43 omega   48.00   75.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000   30.0000 27

 44 omega  143.00  170.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000    0.0000 27

 45 omega   51.00  121.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000  -60.0000 70

 46 omega   77.00  102.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   77.0000    0.0000 25

 47 omega   82.00  129.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000   90.0000 47
;
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
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_diffrn_orient_matrix_UB_12      0.0736973000
_diffrn_orient_matrix_UB_13      -0.0257966000
_diffrn_orient_matrix_UB_21      0.0963025000
_diffrn_orient_matrix_UB_22      -0.0867271000
_diffrn_orient_matrix_UB_23      -0.0263565000
_diffrn_orient_matrix_UB_31      -0.0750684000
_diffrn_orient_matrix_UB_32      0.0052204000
_diffrn_orient_matrix_UB_33      -0.0743916000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 0.998
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_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            29665
_diffrn_reflns_point_group_measured_fraction_full 0.999
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_diffrn_reflns_theta_full        67.684
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_diffrn_source                   'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.734
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_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_description       irregular
_exptl_crystal_F_000             896
_exptl_crystal_recrystallization_method 'Grown from ethyl acetate / hexanes.'
_exptl_crystal_size_max          0.4225
_exptl_crystal_size_mid          0.2271
_exptl_crystal_size_min          0.2226
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.03(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         4697
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0295
_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^)+(0.0441P)^2^+0.3473P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0755
_refine_ls_wR_factor_ref         0.0763
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                4590
_reflns_number_total             4697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol502586n_si_002.cif
_cod_data_source_block           cs1927
_cod_depositor_comments
'Adding full bibliography for 1517816--1517819.cif.'
_cod_database_code               1517818
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C22 H30 N2 O6'
_chemical_oxdiff_usercomment     'Stephanie Bryson/Carlier (SAA-VII-71)'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C15(H15)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C)
;
_olex2_exptl_crystal_mounting_method
'Mounted on nylon cryoloop with Krytox oil.'
_olex2_submission_original_sample_id SAA-VII-71
_olex2_submission_special_instructions 'No special instructions were received'