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_1553065
_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         'C7 H12 Cl N O2'
_chemical_formula_sum            'C7 H7 Cl N O2'
_chemical_formula_weight         172.59
_chemical_name_systematic
; 
(3RS, 4RS)-N-methoxy-3-chloro-4-hydroxy-2,3,4,7-tetrahydro-1H-azepine  
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-12-18
_audit_creation_method
; 
Olex2 1.2 
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736) 
;
_audit_update_record
;
2014-10-08 deposited with the CCDC.
2015-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.467(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.849(3)
_cell_length_b                   4.7231(5)
_cell_length_c                   14.8643(17)
_cell_measurement_reflns_used    1920
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.57
_cell_measurement_theta_min      2.82
_cell_volume                     1696.6(3)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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      100.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0616
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12847
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.426
_diffrn_reflns_theta_min         1.685
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.400
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0697 before and 0.0500 after correction.'
_exptl_crystal_colour            Clear
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       Block
_exptl_crystal_F_000             712
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
_exptl_crystal_size_max          0.159
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.057
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.073
_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     106
_refine_ls_number_reflns         1736
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0562
_refine_ls_shift/su_max          0.043
_refine_ls_shift/su_mean         0.005
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1475P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1727
_refine_ls_wR_factor_ref         0.1969
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1287
_reflns_number_total             1736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4qo00330f2.cif
_cod_data_source_block           klb008_0m
_cod_database_code               1553065
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.939
_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,H,H,H) groups, All O(H) groups 
2. Uiso/Uaniso restraints and constraints 
O2 \\sim O2A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
3. Others 
 Sof(H7BD)=Sof(H7BE)=Sof(H7BF)=Sof(O2A)=1-FVAR(1) 
 Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(O2)=FVAR(1) 
4.a Ternary CH refined with riding coordinates: 
 C2(H2), C3(H3) 
4.b Secondary CH2 refined with riding coordinates: 
 C1(H1A,H1B), C6(H6A,H6B) 
4.c Me refined with riding coordinates: 
 C7(H7AA,H7AB,H7AC), C7(H7BD,H7BE,H7BF) 
4.d Aromatic/amide H refined with riding coordinates: 
 C4(H4), C5(H5) 
4.e Idealised tetrahedral OH refined as rotating group: 
 O1(H1) 
;