Haber-independent, asymmetric synthesis of the marine alkaloid epi-leptosphaerin from a chitin-derived chiral pool synthon
Sperry, Jonathan; Lau, Michelle; Neville, Jessica; Söhnel, Tilo; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01251K

data_7158797
_publ_section_title
;
 Haber-independent, asymmetric synthesis of the marine alkaloid
 epi-leptosphaerin from a chitin-derived chiral pool synthon
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01251K
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C8 H11 N O5'
_chemical_formula_sum            'C8 H11 N O5'
_chemical_formula_weight         201.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-06-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-06 deposited with the CCDC.	2022-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.0853(2)
_cell_length_b                   6.9127(2)
_cell_length_c                   21.3235(4)
_cell_measurement_reflns_used    4269
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      73.4970
_cell_measurement_theta_min      4.1440
_cell_volume                     896.99(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     28.00  53.00   0.50    0.40    --  100.91 -61.00 120.00   50
  2  \w     29.00  55.00   0.50    0.40    --  100.91 -61.00-150.00   52
  3  \w     28.00  68.00   0.50    0.40    --  100.91 -61.00-120.00   80
  4  \w     23.00  48.00   0.50    0.40    --  100.91 -45.00 120.00   50
  5  \w     24.00  49.00   0.50    0.40    --  100.91 -45.00  60.00   50
  6  \w     23.00  48.00   0.50    0.40    --  100.91 -45.00 -30.00   50
  7  \w     25.00  51.00   0.50    0.40    --  100.91 -45.00  30.00   52
  8  \w     24.00  50.00   0.50    0.40    --  100.91 -45.00-120.00   52
  9  \w     25.00  51.00   0.50    0.40    --  100.91 -45.00 -60.00   52
 10  \w    102.00 178.00   0.50    0.40    --  100.91 111.00 -18.00  152
 11  \w    -26.00   0.00   0.50    0.10    --   47.23 -19.00 150.00   52
 12  \w     97.00 135.00   0.50    0.40    --  100.91  17.00 177.00   76
 13  \w     91.00 117.00   0.50    0.40    --  100.91-147.00  -1.00   52
 14  \w     62.00 104.00   0.50    0.40    --  100.91 -95.00-120.00   84
 15  \w    -43.00  26.00   0.50    0.10    --  -47.23  38.00 -60.00  138
 16  \w     -2.00  28.00   0.50    0.10    --  -47.23  17.00 177.00   60
 17  \w   -101.00 -54.00   0.50    0.40    --  -90.25  77.00-150.00   94
 18  \w    -62.00 -23.00   0.50    0.40    --  -90.25  61.00   0.00   78
 19  \w    -71.00 -41.00   0.50    0.40    --  -90.25  61.00 -30.00   60
 20  \w    -39.00 -14.00   0.50    0.40    --  -90.25  45.00  60.00   50
 21  \w    -47.00 -20.00   0.50    0.40    --  -90.25  45.00  90.00   54
 22  \w   -146.00 -85.00   0.50    0.40    --  -90.25-125.00 164.00  122
 23  \w   -111.00 -86.00   0.50    0.10    --  -47.23-125.00 -90.00   50
 24  \w   -120.00 -76.00   0.50    0.10    --  -47.23-125.00  30.00   88
 25  \w    -99.00 -74.00   0.50    0.10    --  -47.23 -17.00   8.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1023832000
_diffrn_orient_matrix_UB_12      -0.2037362000
_diffrn_orient_matrix_UB_13      -0.0007891000
_diffrn_orient_matrix_UB_21      -0.2257340000
_diffrn_orient_matrix_UB_22      -0.0885994000
_diffrn_orient_matrix_UB_23      0.0158510000
_diffrn_orient_matrix_UB_31      -0.0518346000
_diffrn_orient_matrix_UB_32      -0.0176098000
_diffrn_orient_matrix_UB_33      -0.0704606000
_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  0.0343
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            5090
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.733
_diffrn_reflns_theta_min         4.147
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86813
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.490
_exptl_crystal_description       needle
_exptl_crystal_F_000             424
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.193
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 600 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(14)
_refine_ls_extinction_coef       0.0042(10)
_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   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     137
_refine_ls_number_reflns         1620
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0294
_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^)+(0.0356P)^2^+0.1955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0731
_refine_ls_wR_factor_ref         0.0741
_reflns_Friedel_coverage         0.655
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1558
_reflns_number_total             1620
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01251k2.cif
_cod_data_source_block           jcn_npg11_4
_cod_database_code               7158797
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C8H11NO5
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.881
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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:
 C2(H2), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), N(H)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
;
_shelx_res_checksum              3817
_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 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.793