Synthesis of Malhamensilipin A Exploiting Iterative Epoxidation/Chlorination: Experimental and Computational Analysis of Epoxide-Derived Chloronium Ions
Saska, Jan; Lewis, William; Paton, Robert; Denton, Ross Matthew; Chem. Sci.  (2016) –; doi:10.1039/C6SC03012B

data_1543764
_publ_section_title
;
 Synthesis of Malhamensilipin A Exploiting Iterative
 Epoxidation/Chlorination: Experimental and Computational Analysis of
 Epoxide-Derived Chloronium Ions
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C6SC03012B
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H28 Cl2 O4'
_chemical_formula_sum            'C15 H28 Cl2 O4'
_chemical_formula_weight         343.27
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-08-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_audit_update_record
;
2016-03-24 deposited with the CCDC.
2016-08-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.5540(6)
_cell_length_b                   8.7336(10)
_cell_length_c                   36.980(5)
_cell_measurement_reflns_used    3309
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.0110
_cell_measurement_theta_min      4.8790
_cell_volume                     1793.8(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
;
_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    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
  1 omega  -10.00   32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       37.5554    0.0000    0.0000 42

  2 omega   38.00  123.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       37.5554    0.0000    0.0000 85

  3 omega  -41.00   25.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   45.0000    0.0000 66

  4 omega   35.00   98.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -45.0000 -120.0000 63

  5 omega   31.00   86.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -30.0000    0.0000 55

  6 omega   41.00  134.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -77.0000   90.0000 93

  7 omega   36.00   91.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -30.0000  -60.0000 55

  8 omega   71.00  103.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -94.0000  -90.0000 32

  9 omega   42.00   79.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -30.0000   90.0000 37

 10 omega   34.00   62.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045  -37.0000   70.0000 28

 11 omega   17.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       37.5554   38.0000   90.0000 92

 12 omega   12.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       37.5554   57.0000 -150.0000 94

 13 omega   79.00  173.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045   61.0000   30.0000 94

 14 omega   64.00  178.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045   15.0000  -30.0000 114

 15 omega   84.00  172.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045   30.0000 -150.0000 88

 16 omega   84.00  178.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      104.7045   30.0000  120.0000 94
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.2523981000
_diffrn_orient_matrix_UB_12      -0.0714681000
_diffrn_orient_matrix_UB_13      -0.0033900000
_diffrn_orient_matrix_UB_21      -0.0080233000
_diffrn_orient_matrix_UB_22      0.0448422000
_diffrn_orient_matrix_UB_23      -0.0402267000
_diffrn_orient_matrix_UB_31      0.1146764000
_diffrn_orient_matrix_UB_32      -0.1550939000
_diffrn_orient_matrix_UB_33      -0.0101532000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1037
_diffrn_reflns_av_unetI/netI     0.0817
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            11721
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.388
_diffrn_reflns_theta_min         4.783
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    3.359
_exptl_absorpt_correction_T_max  1.348
_exptl_absorpt_correction_T_min  0.445
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       needle
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.7583
_exptl_crystal_size_mid          0.0861
_exptl_crystal_size_min          0.0217
_refine_diff_density_max         1.446
_refine_diff_density_min         -0.746
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Flack x determined using 1007 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     194
_refine_ls_number_reflns         3611
_refine_ls_number_restraints     168
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.1504
_refine_ls_R_factor_gt           0.1349
_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^)+(0.0905P)^2^+22.9016P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3369
_refine_ls_wR_factor_ref         0.3452
_reflns_Friedel_coverage         0.665
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.944
_reflns_number_gt                3031
_reflns_number_total             3611
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc03012b2.cif
_cod_data_source_block           jsrsce
_cod_database_code               1543764
_nottingham_internal_coll_name   JSRSCE
_nottingham_internal_coll_number 12838
_nottingham_internal_coll_client JS/RD
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '20.0000, 80.0000'
_nottingham_internal_coll_frame_width 1.0000
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 3/2/2014
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 5/8/2014
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C15 H28 Cl2 O4'
_chemical_oxdiff_usercomment
'JSRSCE #12838 IN FOMBLIN FILM ON MICROMOUNT FOR JS/RS'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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. Uiso/Uaniso restraints and constraints
C13 \\sim C12 \\sim C11 \\sim C10 \\sim C9 \\sim C8 \\sim C7: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4), C5(H5)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,
 H11B), C12(H12A,H12B), C14(H14A,H14B)
4.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C)
4.d Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4A)
;
_olex2_exptl_crystal_mounting_method 'mounted in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'