Stereoselective Sequential Spirocyclopropanation/Cloke-Wilson Rearrangement Reactions for Synthesis of <i>trans</i>-β,γ-Disubstituted γ-Butyrolactones Using Alkylidene Meldrum's Acid and Benzyl Halides.
Zhang, Minli; Li, Tong; Cui, Chaoxing; Song, Xixi; Chang, Junbiao; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b02978

data_4037839
_publ_section_title
;
 Stereoselective Sequential Spirocyclopropanation/Cloke-Wilson
 Rearrangement Reactions for Synthesis of <i>trans</i>-\b,\g-Disubstituted
 \g-Butyrolactones Using Alkylidene Meldrum's Acid and Benzyl Halides.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02978
_journal_year                    2020
_chemical_formula_moiety         'C19 H16 Br N O6'
_chemical_formula_sum            'C19 H16 Br N O6'
_chemical_formula_weight         434.24
_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     direct
_audit_creation_date             2019-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                86.435(4)
_cell_angle_beta                 77.596(4)
_cell_angle_gamma                77.317(4)
_cell_formula_units_Z            4
_cell_length_a                   12.4962(6)
_cell_length_b                   12.9370(5)
_cell_length_c                   13.6763(6)
_cell_measurement_reflns_used    4421
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6110
_cell_measurement_theta_min      3.7310
_cell_volume                     2106.40(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -105.00  38.00   1.00    1.10    --  -33.50   0.00  90.00  143
  2  \w      1.00  44.00   1.00    1.10    --   36.47 -57.00   0.00   43
  3  \w     66.00  95.00   1.00    1.10    --   36.47  37.00 -60.00   29
  4  \w     61.00 102.00   1.00    1.10    --   36.47 178.00 -60.00   41
  5  \w     29.00  71.00   1.00    1.10    --   36.47 -99.00-150.00   42
  6  \w     61.00 110.00   1.00    1.10    --   36.47 178.00  30.00   49
  7  \w     41.00 104.00   1.00    1.10    --   36.47  57.00-120.00   63
  8  \w     60.00  87.00   1.00    1.10    --   36.47 178.00  90.00   27
  9  \w     59.00 101.00   1.00    1.10    --   36.47 178.00-150.00   42
 10  \w     -1.00  43.00   1.00    1.10    --   36.47  19.00-150.00   44
 11  \w     82.00 109.00   1.00    1.10    --   36.47  19.00  90.00   27
 12  \w      0.00  26.00   1.00    1.10    --   36.47  19.00  90.00   26
 13  \w     58.00  90.00   1.00    1.10    --   36.47  19.00-150.00   32
 14  \w     66.00  92.00   1.00    1.10    --   36.47 178.00 -90.00   26
 15  \w     17.00  81.00   1.00    1.10    --   36.47-107.00  49.00   64
 16  \w     59.00 132.00   1.00   12.50    --  108.00 -30.00  30.00   73
 17  \w     89.00 178.00   1.00   12.50    --  108.00  45.00-150.00   89
 18  \w     85.00 110.00   1.00   12.50    --  108.00-111.00 120.00   25
 19  \w    109.00 139.00   1.00   12.50    --  108.00 111.00   0.00   30
 20  \w     49.00 128.00   1.00   12.50    --  108.00 -61.00  90.00   79
 21  \w    123.00 172.00   1.00   12.50    --  108.00 111.00  30.00   49
 22  \w     38.00  76.00   1.00   12.50    --  108.00 -94.00-120.00   38
 23  \w     79.00 105.00   1.00   12.50    --  108.00 -94.00-120.00   26
 24  \w     38.00  69.00   1.00   12.50    --  108.00-111.00 120.00   31
 25  \w     38.00 123.00   1.00   12.50    --  108.00 -45.00-120.00   85
 26  \w     91.00 121.00   1.00   12.50    --  108.00 -30.00 -30.00   30
 27  \w    119.00 172.00   1.00   12.50    --  108.00 107.00 147.00   53
 28  \w     95.00 155.00   1.00   12.50    --  108.00  61.00  60.00   60
 29  \w     72.00 111.00   1.00   12.50    --  108.00-111.00-150.00   39
 30  \w     62.00 104.00   1.00   12.50    --  108.00-111.00   0.00   42
 31  \w     44.00  71.00   1.00   12.50    --  108.00 -30.00 -30.00   27
 32  \w     63.00 159.00   1.00   12.50    --  108.00  15.00   0.00   96
 33  \w    112.00 138.00   1.00   12.50    --  108.00 111.00 -60.00   26
 34  \w     44.00  97.00   1.00   12.50    --  108.00 -94.00  60.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1200743000
_diffrn_orient_matrix_UB_12      -0.0444113000
_diffrn_orient_matrix_UB_13      0.0157862000
_diffrn_orient_matrix_UB_21      0.0468629000
_diffrn_orient_matrix_UB_22      0.0233242000
_diffrn_orient_matrix_UB_23      -0.1108961000
_diffrn_orient_matrix_UB_31      0.0081272000
_diffrn_orient_matrix_UB_32      0.1112925000
_diffrn_orient_matrix_UB_33      0.0275459000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14873
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         3.706
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.946
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86585
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.369
_exptl_crystal_description       prism
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.687
_refine_diff_density_min         -0.707
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         7518
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0593
_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^)+(0.0869P)^2^+0.8729P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1621
_refine_ls_wR_factor_ref         0.1800
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5520
_reflns_number_total             7518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02978_si_002.cif
_cod_data_source_block           201908211
_cod_database_code               4037839
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c20h20n4o4Br1
_shelx_estimated_absorpt_t_max   0.757
_shelx_estimated_absorpt_t_min   0.719
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
Uanis(O4') = Uanis(O4'A)
Uanis(O3') = Uanis(O3'A)
3. Others
 Sof(O3'A)=Sof(O4'A)=1-FVAR(1)
 Sof(O3')=Sof(O4')=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C3'(H3'), C4'(H4')
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C2'(H2'A,H2'B)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C14(H14), C16(H16), C17(H17), C7'(H7'), C9'(H9'),
 C10'(H10'), C14'(H14'), C16'(H16'), C17'(H17')
4.d Idealised Me refined as rotating group:
 C11(H11D,H11E,H11F), C19(H19D,H19E,H19F), C11'(H11A,H11B,H11C), C19'(H19A,
 H19B,H19C)
;
_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 1.198
_oxdiff_exptl_absorpt_empirical_full_min 0.820