Enantioselective construction of branched 1,3-dienyl substituted quaternary carbon stereocenters by asymmetric allenyl Claisen rearrangement.
Liu, Yangbin; Hu, Haipeng; Lin, Lili; Hao, Xiaoyu; Liu, Xiaohua; Feng, Xiaoming; Chemical communications (Cambridge, England) 52 (2016) 11963–11966; doi:10.1039/c6cc06481g

data_7125053
_publ_section_title
;
 Enantioselective construction of branched 1,3-dienyl substituted
 quaternary carbon stereocenters by asymmetric allenyl Claisen
 rearrangement.
;
_journal_issue                   80
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              11963
_journal_page_last               11966
_journal_paper_doi               10.1039/c6cc06481g
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H13 Br I O3'
_chemical_formula_sum            'C16 H13 Br I O3'
_chemical_formula_weight         460.07
_chemical_name_systematic        lactone
_chemical_properties_physical
Air-sensitive,Heat-sensitive,Oxygen-sensitive,Light-sensitive,Photo-sensitive
_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             2016-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-05-16 deposited with the CCDC.
2016-09-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.5432(2)
_cell_length_b                   12.7924(3)
_cell_length_c                   17.2791(5)
_cell_measurement_reflns_used    6171
_cell_measurement_temperature    293.1(2)
_cell_measurement_theta_max      72.4880
_cell_measurement_theta_min      4.3040
_cell_volume                     1667.36(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      air
_diffrn_ambient_temperature      293.1(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -33.00  106.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921    0.0000 -180.0000 139

  2 omega   23.00   90.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000  -60.0000 67

  3 omega   23.00   90.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000   60.0000 67

  4 omega   10.00  104.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000   90.0000 94

  5 omega   23.00   90.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000 -150.0000 67

  6 omega   38.00   91.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 53

  7 omega   39.00  109.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 70

  8 omega   38.00   91.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

  9 omega   38.00   91.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

 10 omega   38.00   91.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 53

 11 omega   40.00   98.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   60.0000 58

 12 omega   40.00   98.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

 13 omega   40.00  135.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -60.0000 95

 14 omega   17.00  105.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921   38.0000 -120.0000 88

 15 omega   20.00  104.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -30.0000 84

 16 omega   10.00  104.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000    0.0000 94

 17 omega   10.00  104.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000 -180.0000 94

 18 omega  -33.00   55.00   1.0000    5.0200
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -38.0000   60.0000 88

 19 omega   70.00  178.00   1.0000   25.0900
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000    0.0000 108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1138800000
_diffrn_orient_matrix_UB_12      0.0901658000
_diffrn_orient_matrix_UB_13      0.0320625000
_diffrn_orient_matrix_UB_21      -0.1694339000
_diffrn_orient_matrix_UB_22      -0.0622596000
_diffrn_orient_matrix_UB_23      -0.0186518000
_diffrn_orient_matrix_UB_31      0.0060356000
_diffrn_orient_matrix_UB_32      -0.0499425000
_diffrn_orient_matrix_UB_33      0.0810807000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0869
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10267
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.070
_diffrn_reflns_theta_max         67.070
_diffrn_reflns_theta_min         4.300
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.959
_exptl_absorpt_correction_T_max  0.090
_exptl_absorpt_correction_T_min  0.009
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.833
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             884
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.8069
_exptl_crystal_size_mid          0.6162
_exptl_crystal_size_min          0.4356
_refine_diff_density_max         0.907
_refine_diff_density_min         -0.787
_refine_diff_density_rms         0.153
_refine_ls_abs_structure_details
;
 Flack x determined using 1111 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2966
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0658
_refine_ls_R_factor_gt           0.0651
_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^)+(0.1263P)^2^+2.4765P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1829
_refine_ls_wR_factor_ref         0.1841
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2900
_reflns_number_total             2966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc06481g2.cif
_cod_data_source_block           1
_cod_database_code               7125053
_chemical_oxdiff_formula         'C64 H52 Br4 I4 O12'
_reflns_odcompleteness_completeness 99.77
_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.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C12(H12), C13(H13), C14(H14), C16(H16)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              76126
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_solvent_exptl_crystal_recrystallization_method Et2O/PE