[1,4]-sigmatropic rearrangement of chiral nitrones and their utilization in the synthesis of new iminosugars.
Malinowski, Maciej; Rowicki, Tomasz; Guzik, Patrycja; Gryszel, Maciej; Łapczyński, Sebastian; Wielechowska, Monika; Czerwińska, Karolina; Madura, Izabela; Sas, Wojciech; Organic & biomolecular chemistry 14 (2015) 470–482; doi:10.1039/c5ob01432h

data_7154802
_publ_section_title
;
 [1,4]-sigmatropic rearrangement of chiral nitrones and their utilization
 in the synthesis of new iminosugars.
;
_journal_issue                   2
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              470
_journal_page_last               482
_journal_paper_doi               10.1039/c5ob01432h
_journal_volume                  14
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H43 N O7 Si'
_chemical_formula_sum            'C23 H43 N O7 Si'
_chemical_formula_weight         473.67
_chemical_name_systematic
(R)-2-((tert-butyldimethylsilyl)oxy)-1-((4R,5S)-5-((4S,6S)-2',2'-dimethyl-7-oxa-1-azaspiro[bicyclo[2.2.1]heptane-2,5'-[1,3]dioxan]-6-yl)-2,2-dimethyl-1,3-dioxolan-4-yl)ethanol
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-30
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)

Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. & Puschmann, H.
 (2009), J. Appl. Cryst. 42, 339-341.

Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122.
;
_audit_update_record
;
2015-10-15 deposited with the CCDC.
2015-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.96665(7)
_cell_length_b                   10.06647(10)
_cell_length_c                   31.8330(3)
_cell_measurement_reflns_used    15581
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.6690
_cell_measurement_theta_min      4.5880
_cell_volume                     2552.88(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 10.3347
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   23.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0321   38.0000   30.0000 60

  2 omega    7.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0321   77.0000   90.0000 108

  3 omega   16.00   42.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -30.0000   30.0000 26

  4 omega   66.00   92.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000   30.0000 26

  5 omega   61.00   89.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000  150.0000 28

  6 omega   20.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000  -60.0000 57

  7 omega   64.00   94.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000   90.0000 30

  8 omega   19.00   44.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000   90.0000 25

  9 omega  123.00  163.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  134.0000   41.0000 40

 10 omega   38.00   64.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -77.0000  120.0000 26

 11 omega   70.00   97.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -77.0000  120.0000 27

 12 omega   60.00   97.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   90.0000 37

 13 omega  123.00  149.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   90.0000 26

 14 omega   20.00   57.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -30.0000  -30.0000 37

 15 omega   71.00   96.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000 -180.0000 25

 16 omega   63.00  142.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  120.0000 79

 17 omega   21.00   55.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000   30.0000 34

 18 omega   75.00  157.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  125.0000   60.0000 82

 19 omega   46.00   72.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000  -30.0000 26

 20 omega   14.00   62.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -95.0000  -90.0000 48

 21 omega   88.00  114.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   45.0000   60.0000 26

 22 omega   63.00  110.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -88.0000   35.5318 47

 23 omega  -71.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0321   57.0000 -150.0000 104

 24 omega -104.00  -24.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0321  135.0000 -138.0000 80

 25 omega   15.00  117.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0321   38.0000 -150.0000 102

 26 omega   11.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0321   57.0000  -90.0000 104

 27 omega   62.00   90.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   61.0000 -120.0000 28

 28 omega   43.00  174.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   18.0000    1.0000 131
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0066349000
_diffrn_orient_matrix_UB_12      -0.0220117000
_diffrn_orient_matrix_UB_13      -0.0478634000
_diffrn_orient_matrix_UB_21      -0.0450238000
_diffrn_orient_matrix_UB_22      -0.1471227000
_diffrn_orient_matrix_UB_23      0.0071465000
_diffrn_orient_matrix_UB_31      -0.1879387000
_diffrn_orient_matrix_UB_32      0.0359705000
_diffrn_orient_matrix_UB_33      -0.0000331000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            22949
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.680
_diffrn_reflns_theta_max         66.680
_diffrn_reflns_theta_min         4.607
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.154
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies, 
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) 
(compiled Jan 14 2014,18:38:05) 
Empirical absorption correction using spherical harmonics, 
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       prism
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1844 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(10)
_refine_ls_extinction_coef       0.00102(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         4512
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0416P)^2^+0.5848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0713
_refine_ls_wR_factor_ref         0.0720
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4423
_reflns_number_total             4512
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ob01432h2.cif
_cod_data_source_block           13
_cod_depositor_comments
'Adding full bibliography for 7154801--7154802.cif.'
_cod_database_code               7154802
_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:
 C1(H1A), C2(H2), C10(H10), C14(H14), C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C16(H16A,H16B), C17(H17A,H17B), C19(H19A,H19B), C20(H20A,H20B)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              8624