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_1517819
_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         'C19 H26 N2 O4'
_chemical_formula_sum            'C19 H26 N2 O4'
_chemical_formula_weight         346.42
_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
_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            8
_cell_length_a                   11.7191(2)
_cell_length_b                   14.4137(3)
_cell_length_c                   22.2809(4)
_cell_measurement_reflns_used    8259
_cell_measurement_temperature    99.90(14)
_cell_measurement_theta_max      76.0216
_cell_measurement_theta_min      3.6492
_cell_volume                     3763.59(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.90(14)
_diffrn_detector_area_resol_mean 10.4372
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
  1 omega -121.00  -80.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.6052  -99.0000  120.0000 41

  2 omega  -76.00   39.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.6052   19.0000 -180.0000 115

  3 omega   44.00   99.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       41.6052 -125.0000 -180.0000 55

  4 omega   54.00  136.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  150.0000 82

  5 omega   35.00   89.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   90.0000 54

  6 omega  106.00  177.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  110.0000 -155.0000 71

  7 omega   43.00   92.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  153.0000 49

  8 omega  106.00  177.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000 -180.0000 71

  9 omega   90.00  176.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000    0.0000 86

 10 omega  151.00  177.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000   60.0000 26

 11 omega   29.00   43.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  120.0000 14
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1182657000
_diffrn_orient_matrix_UB_12      0.0398117000
_diffrn_orient_matrix_UB_13      0.0160807000
_diffrn_orient_matrix_UB_21      0.0508476000
_diffrn_orient_matrix_UB_22      0.0453629000
_diffrn_orient_matrix_UB_23      0.0566894000
_diffrn_orient_matrix_UB_31      0.0269744000
_diffrn_orient_matrix_UB_32      0.0881226000
_diffrn_orient_matrix_UB_33      -0.0361901000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            14818
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        75.000
_diffrn_reflns_theta_max         76.214
_diffrn_reflns_theta_min         3.652
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.699
_exptl_absorpt_correction_T_max  1.051
_exptl_absorpt_correction_T_min  0.884
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
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    1.223
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1488
_exptl_crystal_recrystallization_method
'Crystals were large prisms. Cut a prism into an irregular shape.'
_exptl_crystal_size_max          0.2561
_exptl_crystal_size_mid          0.1596
_exptl_crystal_size_min          0.0871
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.07(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     640
_refine_ls_number_reflns         7466
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0382
_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^)+(0.0409P)^2^+0.5950P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0940
_reflns_Friedel_coverage         0.795
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                7159
_reflns_number_total             7466
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol502586n_si_004.cif
_cod_data_source_block           cs1831
_cod_depositor_comments
'Adding full bibliography for 1517816--1517819.cif.'
_cod_database_code               1517819
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C19 H26 N2 O4'
_chemical_oxdiff_usercomment     'Stephanie Bryson/Carlier (SAB-V-187)'
_reflns_odcompleteness_completeness 98.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C35A \\sim C35B \\sim C20A \\sim C20B: within 0.6A with sigma of 0.01 and sigma
for terminal atoms of 0.02
3. Others
 Sof(H30C)=Sof(H30D)=Sof(O5B)=Sof(O7B)=Sof(O6B)=Sof(O8B)=Sof(N4B)=Sof(C20B)=
 Sof(C21B)=Sof(H21B)=Sof(C22B)=Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=
 Sof(H25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=Sof(C29B)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C34B)=Sof(C35B)=Sof(C36B)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C37B)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C38B)=Sof(H38D)=
 Sof(H38E)=Sof(H38F)=1-FVAR(1)
 Sof(H30A)=Sof(H30B)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=Sof(N4A)=Sof(C20A)=
 Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C29A)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=Sof(C34A)=Sof(C35A)=Sof(C36A)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38A)=Sof(H38A)=
 Sof(H38B)=Sof(H38C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C2(H2), C12(H12), C31(H31), C21A(H21A), C21B(H21B)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C30(H30A,H30B), C30(H30C,H30D)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C24A(H24A), C25A(H25A), C26A(H26A),
 C27A(H27A), C24B(H24B), C25B(H25B), C26B(H26B), C27B(H27B)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C29A(H29A,H29B,H29C), C36A(H36A,H36B,H36C), C37A(H37A,H37B,H37C),
 C38A(H38A,H38B,H38C), C29B(H29D,H29E,H29F), C36B(H36D,H36E,H36F), C37B(H37D,
 H37E,H37F), C38B(H38D,H38E,H38F)
;
_olex2_exptl_crystal_mounting_method 'Nylon loop with Krytox Oil'
_olex2_submission_original_sample_id SAB-V-187
_olex2_submission_special_instructions 'No special instructions were received'