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_7117950
_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             2015-06-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-07-13 deposited with the CCDC.
2015-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.221(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0556(2)
_cell_length_b                   23.0371(5)
_cell_length_c                   10.8204(3)
_cell_measurement_reflns_used    7889
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      78.0570
_cell_measurement_theta_min      3.8160
_cell_volume                     2406.78(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
  1 omega -107.00  -13.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -57.0000 -120.0000 94

  2 omega  -64.00   30.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   57.0000   30.0000 94

  3 omega   35.00  109.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -95.0000    0.0000 74

  4 omega   41.00   91.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000 -120.0000 50

  5 omega   41.00   91.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000  -30.0000 50

  6 omega   41.00   91.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000  120.0000 50

  7 omega  100.00  178.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  111.0000    0.0000 78

  8 omega   93.00  178.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   30.0000   90.0000 85

  9 omega  100.00  178.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  111.0000   30.0000 78

 10 omega   13.00  115.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.3790   77.0000   30.0000 102

 11 omega  -25.00   69.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.3790  -57.0000  120.0000 94

 12 omega   93.00  173.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   30.0000  -60.0000 80

 13 omega   46.00   98.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000   30.0000 52

 14 omega   41.00  116.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000 -180.0000 75

 15 omega   93.00  178.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   30.0000 -180.0000 85

 16 omega  -50.00   33.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   38.0000  -60.0000 83

 17 omega   18.00  112.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       43.3790   57.0000  150.0000 94

 18 omega   74.00   94.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   15.0000   30.0000 20
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0857872000
_diffrn_orient_matrix_UB_12      0.0321517000
_diffrn_orient_matrix_UB_13      0.1210362000
_diffrn_orient_matrix_UB_21      -0.1345391000
_diffrn_orient_matrix_UB_22      0.0210321000
_diffrn_orient_matrix_UB_23      0.0273178000
_diffrn_orient_matrix_UB_31      -0.0013005000
_diffrn_orient_matrix_UB_32      -0.0546782000
_diffrn_orient_matrix_UB_33      0.0813154000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            19755
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.932
_diffrn_reflns_theta_min         3.838
_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  0.82476
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.243
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.277
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         5102
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0553P)^2^+0.4731P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1136
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4150
_reflns_number_total             5102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc06323j2.cif
_cod_data_source_block           sua1
_cod_database_code               7117950
_chemical_oxdiff_formula         'C20 H20 N2 O2 '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'