Easy access to constrained peptidomimetics and 2,2-disubstituted azetidines by the unexpected reactivity profile of alpha-lithiated N-Boc-azetidines
Giovanna Parisi; Emanuela Capitanelli; Antonella Pierro; Giuseppe Romanazzi; Guy J. Clarkson; Leonardo Degennaro; Renzo Luisi; Chem.Commun. 51 (2015) 15588–; doi:10.1039/C5cc06323J

data_7117949
_publ_section_title
;
 Easy access to constrained peptidomimetics and 2,2-disubstituted
 azetidines by the unexpected reactivity profile of alpha-lithiated
 N-Boc-azetidines
;
_journal_name_full               Chem.Commun.
_journal_page_first              15588
_journal_paper_doi               10.1039/C5cc06323J
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C27 H34 N2 O4'
_chemical_formula_sum            'C27 H34 N2 O4'
_chemical_formula_weight         450.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   other
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2015-07-13 deposited with the CCDC.
2015-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.495(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0493(5)
_cell_length_b                   6.6839(2)
_cell_length_c                   24.3241(10)
_cell_measurement_reflns_used    1555
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      76.7400
_cell_measurement_theta_min      3.7820
_cell_volume                     2405.78(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      180(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_details
;
  1 omega  -66.00  -33.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   57.0000   90.0000 33

  2 omega  -50.00   32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000 -150.0000 82

  3 omega    6.00   31.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   57.0000   90.0000 25

  4 omega  -47.00   33.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000  -30.0000 80

  5 omega  -45.00  -19.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.7109   38.0000  -60.0000 26

  6 omega   41.00   78.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000  -90.0000 37

  7 omega   48.00   96.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000  120.0000 48

  8 omega   38.00   70.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000   90.0000 32

  9 omega  109.00  178.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   45.0000 -180.0000 69

 10 omega   88.00  178.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   45.0000 -120.0000 90

 11 omega   62.00   93.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000  -60.0000 31

 12 omega   85.00  178.00   1.0000   82.5000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   61.0000  120.0000 93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0389974000
_diffrn_orient_matrix_UB_12      0.1635886000
_diffrn_orient_matrix_UB_13      -0.0334208000
_diffrn_orient_matrix_UB_21      -0.0925397000
_diffrn_orient_matrix_UB_22      0.0211217000
_diffrn_orient_matrix_UB_23      -0.0388812000
_diffrn_orient_matrix_UB_31      -0.0275443000
_diffrn_orient_matrix_UB_32      0.1608767000
_diffrn_orient_matrix_UB_33      0.0390019000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0515
_diffrn_reflns_av_unetI/netI     0.0780
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            8764
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.079
_diffrn_reflns_theta_min         3.788
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96420
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.219
_refine_diff_density_min         -0.167
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         4971
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0841
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0291P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1218
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3321
_reflns_number_total             4971
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc06323j2.cif
_cod_data_source_block           vn1
_cod_original_cell_volume        2405.77(16)
_cod_database_code               7117949
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_reflns_odcompleteness_completeness 99.08
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C19(H19A,H19B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C23(H23), C24(H24),
 C25(H25), C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C)
;
_olex2_submission_special_instructions 'No special instructions were received'