Stereochemical studies of the opening of chloro vinyl epoxides: cyclic chloronium ions as intermediates.
Shemet, Andrej; Sarlah, David; Carreira, Erick M.; Organic letters 17 (2015) 1878–1881; doi:10.1021/acs.orglett.5b00558

data_1554900
_publ_section_title
;
 Stereochemical studies of the opening of chloro vinyl epoxides: cyclic
 chloronium ions as intermediates.
;
_journal_issue                   8
_journal_name_full               'Organic letters'
_journal_page_first              1878
_journal_page_last               1881
_journal_paper_doi               10.1021/acs.orglett.5b00558
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H18 Cl N O8 S'
_chemical_formula_sum            'C14 H18 Cl N O8 S'
_chemical_formula_weight         395.80
_chemical_name_systematic
'(2S,3R,5R)-ethyl 5-chloro-3-hydroxy-2-(((4-nitrophenyl)sulfonyl)oxy)hexanoate'
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-04-15
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr  9 2013 14:10:59, GUI svn.r4458)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.1403(10)
_cell_length_b                   13.657(3)
_cell_length_c                   20.719(4)
_cell_measurement_reflns_used    3003
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.82
_cell_measurement_theta_min      2.47
_cell_volume                     1737.5(6)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.04
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0520
_diffrn_reflns_av_unetI/netI     0.0663
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            12689
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.492
_diffrn_reflns_theta_min         1.786
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.383
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6707
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0443 before and 0.0381 after correction.
The Ratio of minimum to maximum transmission is 0.8995.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.513
_exptl_crystal_description       needle
_exptl_crystal_F_000             824
_exptl_crystal_recrystallization_method
'crystallized from a dichloromethane/hexane mixture'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 1054 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3963
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0649
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0329P)^2^+0.1917P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0738
_refine_ls_wR_factor_ref         0.0828
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                3078
_reflns_number_total             3963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b00558_si_003.cif
_cod_data_source_block           ca110413_0m
_cod_original_cell_volume        1737.4(5)
_cod_database_code               1554900
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C9(H9), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C)
2.e Idealised tetrahedral OH refined as rotating group:
 O8(H8)
;
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.862
_shelx_hkl_checksum              88028
_shelx_res_checksum              38740
_shelxl_version_number           2012-9