Organocatalytic Access to a <i>cis</i>-Cyclopentyl-γ-amino Acid: An Intriguing Model of Selectivity and Formation of a Stable 10/12-Helix from the Corresponding γ/α-Peptide.
Fanelli, Rossana; Berta, Dénes; Földes, Tamás; Rosta, Edina; Atkinson, Robert Andrew; Hofmann, Hans-Jörg; Shankland, Kenneth; Cobb, Alexander J. A.; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b10861

data_4133860
_publ_section_title
;
 Organocatalytic Access to a <i>cis</i>-Cyclopentyl-\g-amino Acid: An
 Intriguing Model of Selectivity and Formation of a Stable 10/12-Helix
 from the Corresponding \g/\a-Peptide.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b10861
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H32 N2 O5'
_chemical_formula_sum            'C22 H32 N2 O5'
_chemical_formula_weight         404.49
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.440(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.03210(10)
_cell_length_b                   18.5414(4)
_cell_length_c                   11.6101(2)
_cell_measurement_reflns_used    8765
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.5410
_cell_measurement_theta_min      3.7930
_cell_volume                     1080.00(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -25.00  60.00   0.50    1.50    --   47.95 -38.00-120.00  170
  2  \w     17.00  49.00   0.50    1.50    --   47.95 -99.00-150.00   64
  3  \w     41.00 102.00   0.50    1.50    --   47.95-136.00 -73.00  122
  4  \w     56.00  81.00   0.50    7.00    --  107.75-136.00 -73.00   50
  5  \w     52.00  77.00   0.50    7.00    --  107.75 -88.00-114.22   50
  6  \w     90.00 126.00   0.50    7.00    --  107.75 -88.00-114.22   72
  7  \w     86.00 113.00   0.50    7.00    --  107.75 -61.00 -90.00   54
  8  \w     69.00  97.00   0.50    7.00    --  107.75 -61.00 -30.00   56
  9  \w     71.00 106.00   0.50    7.00    --  107.75 -94.00   0.00   70
 10  \w     73.00 110.00   0.50    7.00    --  107.75-125.00  30.00   74
 11  \w     66.00 118.00   0.50    7.00    --  107.75-133.00 105.00  104
 12  \w     89.00 114.00   0.50    7.00    --  107.75 -88.00 156.15   50
 13  \w     88.00 121.00   0.50    7.00    --  107.75 -30.00  90.00   66
 14  \w     95.00 177.00   0.50    7.00    --  107.75  15.00  60.00  164
 15  \w    153.00 178.00   0.50    7.00    --  107.75  30.00  90.00   50
 16  \w    102.00 128.00   0.50    7.00    --  107.75  30.00  90.00   52
 17  \w     92.00 152.00   0.50    7.00    --  107.75 133.00 172.00  120
 18  \w     88.00 140.00   0.50    7.00    --  107.75 136.00  -8.00  104
 19  \w     95.00 149.00   0.50    7.00    --  107.75  45.00 -90.00  108
 20  \w     59.00 121.00   0.50    7.00    --  107.75 -45.00-150.00  124
 21  \w     61.00 112.00   0.50    7.00    --  107.75 -88.00-173.27  102
 22  \w     63.00 121.00   0.50    7.00    --  107.75 -30.00 -90.00  116
 23  \w     60.00 113.00   0.50    7.00    --  107.75 -88.00  72.12  106
 24  \w     51.00  78.00   0.50    7.00    --  107.75 -30.00  90.00   54
 25  \w     43.00  93.00   0.50    7.00    --  107.75 -61.00  90.00  100
 26  \w     50.00 107.00   0.50    7.00    --  107.75-102.00 167.28  114
 27  \w     39.00 100.00   0.50    1.50    --   47.95-133.00 105.00  122
 28  \w     36.00  63.00   0.50    7.00    --  107.75-125.00  30.00   54
 29  \w     45.00  76.00   0.50    7.00    --  107.75 -94.00  90.00   62
 30  \w     41.00  79.00   0.50    7.00    --  107.75 -94.00 120.00   76
 31  \w     37.00 118.00   0.50    7.00    --  107.75 -15.00  30.00  162
 32  \w     36.00 106.00   0.50    7.00    --  107.75 -94.00-120.00  140
 33  \w     35.00  82.00   0.50    7.00    --  107.75-125.00-150.00   94
 34  \w     34.00 121.00   0.50    7.00    --  107.75 -15.00-150.00  174
 35  \w    -95.00 -19.00   0.50    1.50    --  -47.95 136.00  -8.00  152
 36  \w    -92.00 -17.00   0.50    1.50    --  -47.95 133.00 172.00  150
 37  \w   -118.00 -33.00   0.50    1.50    --  -47.95 -57.00  60.00  170
 38  \w   -104.00 -73.00   0.50    1.50    --  -47.95-125.00 -30.00   62
 39  \w   -115.00 -26.00   0.50    1.50    --  -47.95 -77.00  30.00  178
 40  \w   -120.00 -66.00   0.50    1.50    --  -47.95-136.00 -73.00  108
 41  \w   -120.00 -68.00   0.50    1.50    --  -47.95-133.00 105.00  104
 42  \w   -159.00 -68.00   0.50    7.00    --  -86.25-133.00 105.00  182
 43  \w   -159.00 -66.00   0.50    7.00    --  -86.25-136.00 -73.00  186
 44  \w   -158.00 -99.00   0.50    7.00    --  -86.25 -45.00  30.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0128927000
_diffrn_orient_matrix_UB_12      -0.0629950000
_diffrn_orient_matrix_UB_13      0.0867239000
_diffrn_orient_matrix_UB_21      0.0105305000
_diffrn_orient_matrix_UB_22      0.0541834000
_diffrn_orient_matrix_UB_23      0.1009689000
_diffrn_orient_matrix_UB_31      -0.3064592000
_diffrn_orient_matrix_UB_32      -0.0008340000
_diffrn_orient_matrix_UB_33      -0.0030994000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0575
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            16639
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.047
_diffrn_reflns_theta_max         67.047
_diffrn_reflns_theta_min         3.819
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.716
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65713
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       plate
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.199
_refine_diff_density_min         -0.171
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         3822
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0506P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0828
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.931
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                3560
_reflns_number_total             3822
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10861_si_002.cif
_cod_data_source_block           exp_13
_cod_database_code               4133860
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C22 H32 N2 O5'
_chemical_oxdiff_usercomment     'Needle-like crystal 100 K RF447 f38-39'
_reflns_odcompleteness_completeness 99.90
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C13(H13), C2(H2A)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C5(H5A,H5B), C16(H16A,H16B), C3(H3A,H3B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C22(H22), C21(H21), C19(H19), C18(H18), C20(H20)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C14(H14A,H14B,
 H14C)
;
_shelx_res_checksum              54238
_shelx_hkl_checksum              65833
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.042
_oxdiff_exptl_absorpt_empirical_full_min 0.633