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_1554894
_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         'C6 H12 Cl2 O2'
_chemical_formula_sum            'C6 H12 Cl2 O2'
_chemical_formula_weight         187.06
_chemical_name_systematic        (5R)-2,5-dichlorohexane-1,3-diol
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-03-18
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.030(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.9886(7)
_cell_length_b                   19.578(3)
_cell_length_c                   9.0155(13)
_cell_measurement_reflns_used    9944
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      2.49
_cell_volume                     880.0(2)
_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    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_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  0.0229
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            22528
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.504
_diffrn_reflns_theta_min         2.080
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  0.9502
_exptl_absorpt_correction_T_min  0.8815
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0409 before and 0.0370 after correction.
The Ratio of minimum to maximum transmission is 0.9277.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            '? yellow'
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       needle
_exptl_crystal_F_000             392
_exptl_crystal_recrystallization_method 'crystallized from dichloromethane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.270
_refine_diff_density_min         -0.162
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     187
_refine_ls_number_reflns         4062
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0203
_refine_ls_R_factor_gt           0.0190
_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^)+(0.0279P)^2^+0.0940P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0479
_refine_ls_wR_factor_ref         0.0484
_reflns_Friedel_coverage         0.942
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3945
_reflns_number_total             4062
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b00558_si_004.cif
_cod_data_source_block           ca120313_result
_cod_database_code               1554894
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H10A,H10B} of C10, {H9A,H9B} of C9, {H8A,H8B} of C8, H4A of C4, H5 of C5,
  H6 of C6, H7 of C7, H1 of C1, H2A of C2, {H3A,H3B} of C3
 At 1.5 times of:
  {H12A,H12B,H12C} of C12, {H11A,H11B,H11C} of C11, H2 of O2, H3 of O3, H4 of
  O4, H1A of O1
2.a Ternary CH refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C1(H1), C2(H2A), C4(H4A)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1A), O2(H2), O3(H3), O4(H4)
;
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.876
_shelx_hkl_checksum              9292
_shelx_res_checksum              38068
_shelxl_version_number           2012-9