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_1517817
_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         'C18 H24 N2 O4'
_chemical_formula_sum            'C18 H24 N2 O4'
_chemical_formula_weight         332.39
_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
_audit_creation_date             2014-08-18
_audit_creation_method
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Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.3302(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.53990(16)
_cell_length_b                   16.39067(19)
_cell_length_c                   10.65777(14)
_cell_measurement_reflns_used    10660
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      75.7473
_cell_measurement_theta_min      4.2427
_cell_volume                     1798.72(4)
_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
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(1)
_diffrn_detector_area_resol_mean 8.3174
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_details
;
  1 omega  -56.00   23.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -44.4841   77.0000  120.0000 79

  2 omega   34.00  111.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   37.0000    0.0000 77

  3 omega   40.00   68.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000   30.0000 28

  4 omega   47.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000  120.0000 51

  5 omega  136.00  174.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000  -30.0000 38

  6 omega   31.00  141.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -15.0000  -60.0000 110

  7 omega   43.00  131.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -61.0000  -60.0000 88

  8 omega   39.00   76.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000  -30.0000 37

  9 omega   36.00   90.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000 -150.0000 54

 10 omega   86.00  114.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   61.0000  -30.0000 28

 11 omega   35.00   68.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000   60.0000 33

 12 omega   85.00  116.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   30.0000   90.0000 31

 13 omega   49.00   77.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000   90.0000 28

 14 omega    2.00   97.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841 -125.0000    0.0000 95

 15 omega   22.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   37.0000 -180.0000 93

 16 omega   22.00  113.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   45.0000   76.0000 91

 17 omega   35.00  104.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000  -30.0000 69

 18 omega   84.00  176.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   45.0000  120.0000 92

 19 omega   84.00  109.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   45.0000  -60.0000 25

 20 omega   38.00   77.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000 -180.0000 39
;
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0435349000
_diffrn_orient_matrix_UB_12      -0.0051214000
_diffrn_orient_matrix_UB_13      -0.1472663000
_diffrn_orient_matrix_UB_21      -0.0102574000
_diffrn_orient_matrix_UB_22      0.0937920000
_diffrn_orient_matrix_UB_23      -0.0071371000
_diffrn_orient_matrix_UB_31      0.1426017000
_diffrn_orient_matrix_UB_32      0.0051850000
_diffrn_orient_matrix_UB_33      -0.0124748000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14556
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.925
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         75.936
_diffrn_reflns_theta_min         4.246
_diffrn_source                   'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.711
_exptl_absorpt_correction_T_max  1.740
_exptl_absorpt_correction_T_min  1.110
_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
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;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       needle
_exptl_crystal_F_000             712
_exptl_crystal_recrystallization_method 'Crystallized from CH2Cl2 / hexanes.'
_exptl_crystal_size_max          0.4072
_exptl_crystal_size_mid          0.2822
_exptl_crystal_size_min          0.0512
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2869 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.14(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         6963
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0541P)^2^+0.6015P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.1107
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.947
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_reflns_number_gt                6597
_reflns_number_total             6963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol502586n_si_003.cif
_cod_data_source_block           cs1909
_cod_depositor_comments
'Adding full bibliography for 1517816--1517819.cif.'
_cod_database_code               1517817
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C18 H24 N2 O4'
_chemical_oxdiff_usercomment     'Stephanie Bryson/Carlier (SAA-VII-15)'
_reflns_odcompleteness_completeness 98.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C16(H16), C34(H34)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C5(H5), C6(H6), C7(H7), C8(H8), N4(H4), C23(H23), C24(H24), C25(H25),
 C26(H26)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C28(H28A,H28B,H28C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C)
;
_olex2_exptl_crystal_mounting_method 'Mounted on cryloop with Krytox oil.'
_olex2_submission_original_sample_id SAA-VII-15
_olex2_submission_special_instructions 'No special instructions were received'