Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate.
Sharp, Phillip P.; Mikusek, Jiri; Ho, Junming; Krenske, Elizabeth H.; Banwell, Martin G.; Coote, Michelle L.; Ward, Jas S.; Willis, Anthony C.; The Journal of organic chemistry 83 (2018) 13678–13690; doi:10.1021/acs.joc.8b01766

data_4034861
_publ_section_title
;
 Mechanistic Studies on the Base-Promoted Conversion of
 Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans:
 Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl
 Ylide Intermediate.
;
_journal_issue                   22
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13678
_journal_page_last               13690
_journal_paper_doi               10.1021/acs.joc.8b01766
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C10 H13 Br2 Cl O'
_chemical_formula_sum            'C10 H13 Br2 Cl O'
_chemical_formula_weight         344.47
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                83.085(6)
_cell_angle_beta                 86.309(6)
_cell_angle_gamma                81.870(6)
_cell_formula_units_Z            2
_cell_length_a                   7.4888(5)
_cell_length_b                   8.8924(6)
_cell_length_c                   9.2043(6)
_cell_measurement_reflns_used    1581
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      29.0860
_cell_measurement_theta_min      4.4330
_cell_volume                     601.67(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3744
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.795
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -79.00  12.00   1.00    3.50    --  -11.22 -57.00 -60.00   91
  2  \w    -75.00  14.00   1.00    3.50    --  -11.22 -77.00-180.00   89
  3  \w    -39.00  61.00   1.00    3.50    --  -11.22  57.00  90.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0712556000
_diffrn_orient_matrix_UB_12      0.0114231000
_diffrn_orient_matrix_UB_13      -0.0490002000
_diffrn_orient_matrix_UB_21      -0.0533839000
_diffrn_orient_matrix_UB_22      0.0473102000
_diffrn_orient_matrix_UB_23      0.0476095000
_diffrn_orient_matrix_UB_31      0.0353295000
_diffrn_orient_matrix_UB_32      0.0648607000
_diffrn_orient_matrix_UB_33      -0.0370426000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0625
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.795
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            4866
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.795
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.122
_diffrn_reflns_theta_min         3.403
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.925
_exptl_absorpt_correction_T_max  0.48372
_exptl_absorpt_correction_T_min  0.47280
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.901
_exptl_crystal_description       plate
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.565
_exptl_crystal_size_mid          0.335
_exptl_crystal_size_min          0.098
_exptl_crystal_size_rad          0.073
_refine_diff_density_max         0.700
_refine_diff_density_min         -0.986
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     128
_refine_ls_number_reflns         2828
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0380P)^2^+0.0565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0820
_refine_ls_wR_factor_ref         0.0982
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2142
_reflns_number_total             2828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01766_si_004.cif
_cod_data_source_block           JM-PSF-10_scale
_cod_database_code               4034861
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2.a Ternary CH refined with riding coordinates:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              87257
_shelx_hkl_checksum              19886
_ins_header
;
TITL JM-PSF-10_scale in P-1 
REM P-1 (#2 in standard setting)
CELL 0.71073   7.488760   8.892429   9.204332  83.0853  86.3085  81.8699
ZERR    2.00   0.000512   0.000592   0.000630   0.0056   0.0056   0.0056
LATT  1
SFAC C H O Cl Br
UNIT 20.00 26.00 2.00 2.00 4.00
TREF
HKLF 4
END
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.577
_oxdiff_exptl_absorpt_empirical_full_min 0.526