Expanding the scope of the successive ring expansion strategy for macrocycle and medium-sized ring synthesis: unreactive and reactive lactams.
Yang, Zhongzhen; Arnoux, Marion; Hazelard, Damien; Hughes, Owen R.; Nabarro, Joe; Whitwood, Adrian C.; Fascione, Martin A.; Spicer, Christopher D.; Compain, Philippe; Unsworth, William P.; Organic & biomolecular chemistry 22 (2024) 2985–2991; doi:10.1039/d4ob00285g

data_7159852
_publ_section_title
;
 Expanding the scope of the successive ring expansion strategy for
 macrocycle and medium-sized ring synthesis: unreactive and reactive
 lactams.
;
_journal_issue                   15
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2985
_journal_page_last               2991
_journal_paper_doi               10.1039/d4ob00285g
_journal_volume                  22
_journal_year                    2024
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C9 H15 N O7'
_chemical_formula_sum            'C9 H15 N O7'
_chemical_formula_weight         249.22
_chemical_name_systematic
3,4,5-Trihydroxy-6-(hydroxymethyl)-1-(3-hydroxypropanoyl)piperidin-2-one
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2023-10-25 deposited with the CCDC.	2024-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.987(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.16094(17)
_cell_length_b                   12.6912(4)
_cell_length_c                   8.2512(3)
_cell_measurement_reflns_used    1922
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      70.6960
_cell_measurement_theta_min      6.3840
_cell_volume                     539.71(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.107a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.107a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.107a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -20.00  22.00   1.00    1.00    --    0.00 -77.00   0.00   42
  2  \w    -20.00  13.00   1.00    1.00    --    0.00 -77.00-120.00   33
  3  \w    -19.00   9.00   1.00    1.00    --    0.00 -77.00 -90.00   28
  4  \w     15.00  60.00   1.00    4.00    --   54.00 -57.00 -60.00   45
  5  \w    -15.00  75.00   1.00    4.00    --   54.00 -38.00-180.00   90
  6  \w      5.00  82.00   1.00    4.00    --   54.00 -77.00  90.00   77
  7  \w     39.00  71.00   1.00    4.00    --   54.00 -57.00 -30.00   32
  8  \w     25.00  81.00   1.00    4.00    --   54.00 -77.00-120.00   56
  9  \w     44.00 122.00   1.00    4.00    --   54.00  38.00   0.00   78
 10  \w     34.00 103.00   1.00    4.00    --   54.00  57.00 -90.00   69
 11  \w     62.00  92.00   1.00    4.00    --  108.00 178.00-150.00   30
 12  \w     72.00 103.00   1.00    4.00    --  108.00 -91.00-180.00   31
 13  \w    153.00 178.00   1.00    4.00    --  108.00  77.00-120.00   25
 14  \w    105.00 141.00   1.00    4.00    --  108.00 178.00-150.00   36
 15  \w     41.00  66.00   1.00    4.00    --  108.00 -91.00   0.00   25
 16  \w     39.00  69.00   1.00    4.00    --  108.00 -91.00-180.00   30
 17  \w     53.00 100.00   1.00    4.00    --  108.00 -50.00 150.00   47
 18  \w     73.00 100.00   1.00    4.00    --  108.00-111.00   0.00   27
 19  \w     37.00  71.00   1.00    4.00    --  108.00-111.00   0.00   34
 20  \w     48.00 129.00   1.00    4.00    --  108.00 -50.00 -30.00   81
 21  \w     36.00  63.00   1.00    4.00    --  108.00-111.00-180.00   27
 22  \w     77.00 106.00   1.00    4.00    --  108.00-111.00-180.00   29
 23  \w     67.00 142.00   1.00    4.00    --  108.00 178.00  30.00   75
 24  \w     78.00 105.00   1.00    4.00    --  108.00 -91.00   0.00   27
 25  \w    150.00 176.00   1.00    4.00    --  108.00  50.00 -30.00   26
 26  \w    106.00 137.00   1.00    4.00    --  108.00  77.00-120.00   31
 27  \w     86.00 117.00   1.00    4.00    --  108.00  50.00 -30.00   31
 28  \w    101.00 128.00   1.00    4.00    --  108.00 -50.00 150.00   27
 29  \w    142.00 168.00   1.00    4.00    --  108.00  77.00   0.00   26
 30  \w     93.00 178.00   1.00    4.00    --  108.00  50.00 -60.00   85
 31  \w     78.00 178.00   1.00    4.00    --  108.00  25.00  30.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1024879000
_diffrn_orient_matrix_UB_12      -0.0278455000
_diffrn_orient_matrix_UB_13      -0.1733907000
_diffrn_orient_matrix_UB_21      0.0379086000
_diffrn_orient_matrix_UB_22      0.1153076000
_diffrn_orient_matrix_UB_23      -0.0522520000
_diffrn_orient_matrix_UB_31      0.2782756000
_diffrn_orient_matrix_UB_32      -0.0258683000
_diffrn_orient_matrix_UB_33      -0.0462219000
_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  0.0241
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            3325
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.041
_diffrn_reflns_theta_max         67.041
_diffrn_reflns_theta_min         5.368
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.156
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.807
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.107a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_description       plate
_exptl_crystal_F_000             264
_exptl_crystal_recrystallization_method
'crystallisation from ethyl acetate and methanol'
_exptl_crystal_size_max          0.177
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 796 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(12)
_refine_ls_extinction_coef       0.0034(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         1922
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0326
_refine_ls_R_factor_gt           0.0292
_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^)+(0.0293P)^2^+0.0753P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0651
_refine_ls_wR_factor_ref         0.0674
_reflns_Friedel_coverage         0.903
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                1810
_reflns_number_total             1922
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00285g2.cif
_cod_data_source_block           wpu21009
_cod_depositor_comments          'Adding full bibliography for 7159852.cif.'
_cod_database_code               7159852
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C9 H15 N1 O7'
_chemical_oxdiff_usercomment     'Zhongzhen Yang YZZ0428-R1'
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.822
_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
2.a Ternary CH refined with riding coordinates:
 C3(H3A), C2(H2A), C5(H5), C4(H4A)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C9(H9A,H9B), C8(H8A,H8B)
;
_shelx_res_checksum              68174
_olex2_date_sample_data_collection 2021-05-06
_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 1.198
_oxdiff_exptl_absorpt_empirical_full_min 0.812