Facile synthesis of new N-(aminocycloalkylene)amino acid compounds using chiral triflate esters with N-Boc-aminopyrrolidines and N-Boc-aminopiperidines
Matulevičiūtė, Gita; Kleizienė, Neringa; Račkauskienė, Greta; Martynaitis, Vytas; Bieliauskas, Aurimas; Šachlevičiūtė, Urtė; Jankauskas, Rokas; Bartkus, Martynas R.; Sløk, Frank A.; Šačkus, Algirdas; RSC Advances 13 (2023) 21378–21394; doi:10.1039/D3RA03060A

data_7247063
_publ_section_title
;
 Facile synthesis of new N-(aminocycloalkylene)amino acid compounds using
 chiral triflate esters with N-Boc-aminopyrrolidines and
 N-Boc-aminopiperidines
;
_journal_issue                   31
_journal_name_full               'RSC Advances'
_journal_page_first              21378
_journal_page_last               21394
_journal_paper_doi               10.1039/D3RA03060A
_journal_volume                  13
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H30 N2 O4'
_chemical_formula_sum            'C16 H30 N2 O4'
_chemical_formula_weight         314.43
_chemical_name_systematic
'tert-butyl 1-((S)-1-(methoxycarbonyl)-2-methylpropyl)piperidin-4-ylcarbamate'
_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_Int_Tables_number      4
_audit_creation_date             2021-11-19
_audit_creation_method
;
Olex2 1.2-ac4
(compiled 2018.05.17 svn.r3504 for Rigaku Oxford Diffraction, GUI svn.r5492)
;
_audit_update_record
;
2023-03-07 deposited with the CCDC.	2023-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.4248(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.09241(17)
_cell_length_b                   12.82419(17)
_cell_length_c                   14.0647(2)
_cell_measurement_reflns_used    28510
_cell_measurement_temperature    150.0(1)
_cell_measurement_theta_max      77.1470
_cell_measurement_theta_min      3.1530
_cell_volume                     1805.09(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9802
_diffrn_measured_fraction_theta_max 0.8260
_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    -79.00  11.00   0.50    0.33    --  -49.92 102.00  68.00  180
  2  \w     13.00  72.00   0.50    0.33    --   49.92-102.00 -34.00  118
  3  \w    -71.00 -46.00   0.50    1.25    --  -84.25 102.00  68.00   50
  4  \w   -145.00-120.00   0.50    1.25    --  -84.25-102.00 -34.00   50
  5  \w    152.00 177.00   0.50    1.25    --  105.75 102.00  68.00   50
  6  \w     57.00 106.00   0.50    1.25    --  105.75-102.00 -34.00   98
  7  \w   -120.00 -93.00   0.50    0.33    --  -49.92 -77.00  90.00   54
  8  \w    -49.00   9.00   0.50    0.33    --  -49.92  38.00 -30.00  116
  9  \w   -114.00 -87.00   0.50    0.33    --  -49.92-125.00  60.00   54
 10  \w   -116.00 -88.00   0.50    0.33    --  -49.92 -77.00  30.00   56
 11  \w     90.00 116.00   0.50    0.33    --   49.92  77.00  30.00   52
 12  \w     88.00 118.00   0.50    0.33    --   49.92  77.00  60.00   60
 13  \w     88.00 113.00   0.50    0.33    --   49.92  77.00 120.00   50
 14  \w     51.00  78.00   0.50    0.33    --   49.92-125.00  60.00   54
 15  \w    -13.00  38.00   0.50    0.33    --   49.92 -38.00  90.00  102
 16  \w    -45.00 -12.00   0.50    1.25    --  -84.25  15.00 -90.00   66
 17  \w     74.00 106.00   0.50    1.25    --  105.75-101.00 174.70   64
 18  \w     62.00 106.00   0.50    1.25    --  105.75 -94.00 120.00   88
 19  \w     34.00  61.00   0.50    1.25    --  105.75 -94.00 -60.00   54
 20  \w    120.00 175.00   0.50    1.25    --  105.75  77.00 -90.00  110
 21  \w    101.00 152.00   0.50    1.25    --  105.75  45.00  60.00  102
 22  \w     34.00  65.00   0.50    1.25    --  105.75 -61.00-150.00   62
 23  \w     40.00  66.00   0.50    1.25    --  105.75 -61.00-120.00   52
 24  \w     35.00  66.00   0.50    1.25    --  105.75 -61.00 150.00   62
 25  \w     35.00  66.00   0.50    1.25    --  105.75 -61.00 -60.00   62
 26  \w     39.00  66.00   0.50    1.25    --  105.75 -61.00  60.00   54
 27  \w     53.00  80.00   0.50    1.25    --  105.75 -77.00-120.00   54
 28  \w    136.00 176.00   0.50    1.25    --  105.75  15.00-180.00   80
 29  \w     58.00 106.00   0.50    1.25    --  105.75 -94.00-120.00   96
 30  \w     39.00  64.00   0.50    1.25    --  105.75-125.00  60.00   50
 31  \w     69.00 109.00   0.50    1.25    --  105.75-125.00  60.00   80
 32  \w     34.00  61.00   0.50    1.25    --  105.75-101.00 174.70   54
 33  \w     75.00 103.00   0.50    1.25    --  105.75 -94.00  30.00   56
 34  \w    107.00 137.00   0.50    1.25    --  105.75  39.00  21.75   60
 35  \w     66.00  91.00   0.50    1.25    --  105.75 -77.00 -90.00   50
 36  \w     50.00  75.00   0.50    1.25    --  105.75 -77.00-180.00   50
 37  \w     43.00 106.00   0.50    1.25    --  105.75 -94.00   0.00  126
 38  \w     77.00 107.00   0.50    1.25    --  105.75-100.00  89.53   60
 39  \w     38.00  71.00   0.50    1.25    --  105.75 -77.00  30.00   66
 40  \w     50.00  77.00   0.50    1.25    --  105.75 -75.00 129.43   54
 41  \w    134.00 177.00   0.50    1.25    --  105.75  45.00  30.00   86
 42  \w     86.00 111.00   0.50    1.25    --  105.75-125.00  90.00   50
 43  \w    113.00 140.00   0.50    1.25    --  105.75 125.00  90.00   54
 44  \w    111.00 171.00   0.50    1.25    --  105.75  30.00 -90.00  120
 45  \w     72.00  99.00   0.50    1.25    --  105.75-144.00-107.65   54
 46  \w     45.00  77.00   0.50    1.25    --  105.75 -77.00  60.00   64
 47  \w     80.00 105.00   0.50    1.25    --  105.75 -94.00 -90.00   50
 48  \w    145.00 178.00   0.50    1.25    --  105.75 125.00 120.00   66
 49  \w     76.00 105.00   0.50    1.25    --  105.75-119.00   1.38   58
 50  \w     47.00  74.00   0.50    1.25    --  105.75-119.00   1.38   54
 51  \w     82.00 109.00   0.50    1.25    --  105.75-125.00 150.00   54
 52  \w     97.00 176.00   0.50    1.25    --  105.75  45.00 -60.00  158
 53  \w     39.00  72.00   0.50    1.25    --  105.75-125.00  90.00   66
 54  \w     97.00 127.00   0.50    1.25    --  105.75 125.00  30.00   60
 55  \w    150.00 178.00   0.50    1.25    --  105.75 125.00  30.00   56
 56  \w     34.00  61.00   0.50    1.25    --  105.75 -77.00 -30.00   54
 57  \w     95.00 120.00   0.50    1.25    --  105.75  77.00-120.00   50
 58  \w    134.00 169.00   0.50    1.25    --  105.75  77.00-120.00   70
 59  \w     50.00  77.00   0.50    1.25    --  105.75 -80.00 -78.02   54
 60  \w     39.00  66.00   0.50    1.25    --  105.75 -61.00  90.00   54
 61  \w     35.00  68.00   0.50    1.25    --  105.75 -77.00  90.00   66
 62  \w     83.00 108.00   0.50    1.25    --  105.75-125.00 -30.00   50
 63  \w     70.00 107.00   0.50    1.25    --  105.75-100.00-142.90   74
 64  \w    146.00 177.00   0.50    1.25    --  105.75  30.00 -30.00   62
 65  \w    150.00 178.00   0.50    1.25    --  105.75 125.00 -90.00   56
 66  \w     52.00  78.00   0.50    1.25    --  105.75 -88.00 153.03   52
 67  \w     90.00 132.00   0.50    1.25    --  105.75 -88.00 153.03   84
 68  \w     37.00  66.00   0.50    1.25    --  105.75-100.00-142.90   58
 69  \w     95.00 173.00   0.50    1.25    --  105.75  77.00   0.00  156
 70  \w     61.00 108.00   0.50    1.25    --  105.75-109.00-118.61   94
 71  \w     98.00 145.00   0.50    1.25    --  105.75  30.00-150.00   94
 72  \w    153.00 178.00   0.50    1.25    --  105.75  30.00-150.00   50
 73  \w    112.00 140.00   0.50    1.25    --  105.75  30.00   0.00   56
 74  \w    102.00 127.00   0.50    1.25    --  105.75  30.00  60.00   50
 75  \w    103.00 128.00   0.50    1.25    --  105.75  15.00  60.00   50
 76  \w     99.00 128.00   0.50    1.25    --  105.75  45.00   0.00   58
 77  \w    134.00 171.00   0.50    1.25    --  105.75  45.00-150.00   74
 78  \w    101.00 126.00   0.50    1.25    --  105.75  45.00 120.00   50
 79  \w    153.00 178.00   0.50    1.25    --  105.75 125.00-180.00   50
 80  \w    134.00 163.00   0.50    1.25    --  105.75 125.00 -30.00   58
 81  \w     37.00  62.00   0.50    1.25    --  105.75-100.00  89.53   50
 82  \w     93.00 128.00   0.50    1.25    --  105.75  61.00 120.00   70
 83  \w     34.00  83.00   0.50    1.25    --  105.75 -94.00-180.00   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku, 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      -0.0656014000
_diffrn_orient_matrix_UB_12      -0.0315948000
_diffrn_orient_matrix_UB_13      -0.1009312000
_diffrn_orient_matrix_UB_21      0.1392427000
_diffrn_orient_matrix_UB_22      -0.0171270000
_diffrn_orient_matrix_UB_23      -0.0309844000
_diffrn_orient_matrix_UB_31      -0.0031505000
_diffrn_orient_matrix_UB_32      -0.1146038000
_diffrn_orient_matrix_UB_33      0.0325185000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            37496
_diffrn_reflns_theta_full        75.0
_diffrn_reflns_theta_max         77.5
_diffrn_reflns_theta_min         3.17
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.669
_exptl_absorpt_correction_T_max  0.96107
_exptl_absorpt_correction_T_min  0.85913
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.1569
_exptl_crystal_description       'Block '
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.2023
_refine_diff_density_min         -0.1204
_refine_diff_density_rms         0.0271
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.04(9)
_refine_ls_d_res_high            0.7897
_refine_ls_d_res_low             13.9467
_refine_ls_goodness_of_fit_ref   1.0518
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    84
_refine_ls_number_parameters     417
_refine_ls_number_reflns         6342
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.0518
_refine_ls_R_factor_all          0.0316
_refine_ls_R_factor_gt           0.0309
_refine_ls_shift/su_max          0.0065
_refine_ls_shift/su_mean         0.0011
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0520P)^2^+0.1876P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0840
_reflns_Friedel_coverage         0.641
_reflns_limit_h_max              12
_reflns_limit_h_min              -12
_reflns_limit_k_max              13
_reflns_limit_k_min              -16
_reflns_limit_l_max              17
_reflns_limit_l_min              -17
_reflns_number_gt                6171
_reflns_number_total             6342
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3ra03060a2.cif
_cod_data_source_block           GMP575
_cod_depositor_comments
;

2024-12-16
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C32 H60 N4 O8'
_cod_original_formula_weight         628.86
_cod_original_formula_moiety         '2(C16 H30 N2 O4)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        1805.08(5)
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               7247063
_chemical_oxdiff_formula         'C64 H120 N8 O16'
_chemical_oxdiff_usercomment     'GMP-575 (from Vytas)'
_diffrn_oxdiff_digest_frames
;
01cb5de508bc2b420c79b477ab60959dbb000422e40
;
_diffrn_oxdiff_digest_hkl
;
019c02036f9345f24ad799796480352f93c4b2
;
_reflns_odcompleteness_completeness 99.23
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.49
_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
2.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7), C8(H8), C54(H54), C57(H57), C58(H58)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C3(H3a,H3b), C5(H5a,H5b), C6(H6a,H6b), C52(H52a,H52b), C53(H53a,
 H53b), C55(H55a,H55b), C56(H56a,H56b)
2.c Idealised Me refined as rotating group:
 C9(H9a,H9b,H9c), C10(H10a,H10b,H10c), C14(H14a,H14b,H14c), C20(H20a,H20b,
 H20c), C21(H21a,H21b,H21c), C22(H22a,H22b,H22c), C59(H59a,H59b,H59c), C60(H60a,
 H60b,H60c), C64(H64a,H64b,H64c), C70(H70a,H70b,H70c), C71(H71a,H71b,H71c),
 C72(H72a,H72b,H72c)
;
_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 1.346
_oxdiff_exptl_absorpt_empirical_full_min 0.650