New building blocks for iminosugars: a concise synthesis of polyhydroxylated N-alkoxypiperidines through an intramolecular azepine ring contraction
Barnes, Korry L.; Chen, Kelly; Catalano, Vincent J.; Jeffrey, Christopher S.; Organic Chemistry Frontiers 2 (2015) 497–; doi:10.1039/C4QO00330F

data_1553067
_publ_section_title
;
 New building blocks for iminosugars: a concise synthesis of
 polyhydroxylated N-alkoxypiperidines through an intramolecular azepine
 ring contraction
;
_journal_issue                   5
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              497
_journal_paper_doi               10.1039/C4QO00330F
_journal_volume                  2
_journal_year                    2015
_chemical_formula_moiety         'C13 H19 N O5'
_chemical_formula_sum            'C13 H19 N O5'
_chemical_formula_weight         269.29
_chemical_name_systematic
;
(2RS,3RS,4SR,5RS)-N-phenylmethoxy-2-hydroxymethyl-3,4,5-trihydroxypiperidine
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-24
_audit_creation_method
; 
Olex2 1.2 
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874) 
;
_audit_update_record
;
2014-10-08 deposited with the CCDC.
2015-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                112.4571(11)
_cell_angle_beta                 97.7331(11)
_cell_angle_gamma                99.3952(11)
_cell_formula_units_Z            4
_cell_length_a                   5.3906(3)
_cell_length_b                   15.9299(9)
_cell_length_c                   17.3564(10)
_cell_measurement_reflns_used    4557
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.890
_cell_measurement_theta_min      2.291
_cell_volume                     1326.85(13)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      99.65
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            33786
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.593
_diffrn_reflns_theta_min         1.300
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6922
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0672 before and 0.0526 after correction. The Rat'
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.348
_exptl_crystal_description       Block
_exptl_crystal_F_000             576
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
_exptl_crystal_size_max          0.401
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.176
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     376
_refine_ls_number_reflns         8134
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.000
_refine_ls_R_factor_all          0.0775
_refine_ls_R_factor_gt           0.0467
_refine_ls_shift/su_max          0.041
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0710P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1352
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5491
_reflns_number_total             8134
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4qo00330f2.cif
_cod_data_source_block           klb010_0m
_cod_depositor_comments
;

2022-11-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C13 H19 N O5)'
_cod_original_formula_sum        'C26 H38 N2 O10'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     538.58
_cod_database_code               1553067
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.960
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups 
 At 1.5 times of: 
  All O(H) groups 
2. Others 
 Sof(H7bc)=Sof(H7bd)=Sof(C8A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)= 
 Sof(C11A)=Sof(H11A)=Sof(C10A)=Sof(H10A)=Sof(C9A)=Sof(H9A)=1-FVAR(1) 
 Sof(H7aa)=Sof(H7ab)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)= 
 Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=FVAR(1) 
3.a Ternary CH refined with riding coordinates: 
 C2(H2), C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17), C18(H18) 
3.b Secondary CH2 refined with riding coordinates: 
 C1(H1a,H1b), C6(H6a,H6b), C7(H7aa,H7ab), C7(H7bc,H7bd), C14(H14a,H14b), 
 C19(H19a,H19b), C20(H20a,H20b) 
3.c Aromatic/amide H refined with riding coordinates: 
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C13A(H13A), C12A(H12A), 
 C11A(H11A), C10A(H10A), C9A(H9A), C22(H22), C23(H23), C24(H24), C25(H25), 
 C26(H26) 
3.d Fitted hexagon refined as free rotating group: 
 C8(C9,C10,C11,C12,C13), C8A(C13A,C12A,C11A,C10A,C9A), C21(C22,C23,C24,C25,C26) 
3.e Idealised tetrahedral OH refined as rotating group: 
 O2(H2a), O3(H3a), O6(H6), O7(H7), O8(H8), O9(H9b) 
;