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_7125052
_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 rmad
_chemical_formula_moiety         'C18 H19 Br O3'
_chemical_formula_sum            'C18 H19 Br O3'
_chemical_formula_weight         363.24
_chemical_name_systematic        1,3-diene
_chemical_properties_physical    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
_audit_creation_date             2015-09-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.21 svn.r3230 for OlexSys, GUI svn.r5103)
;
_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                   8.7409(4)
_cell_length_b                   12.0555(4)
_cell_length_c                   16.4217(6)
_cell_measurement_reflns_used    4550
_cell_measurement_temperature    292.56(10)
_cell_measurement_theta_max      72.4250
_cell_measurement_theta_min      4.5510
_cell_volume                     1730.45(12)
_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      292.56(10)
_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   17.00  105.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   38.0000 -120.0000 88

  2 omega   17.00  105.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   38.0000  -30.0000 88

  3 omega  -31.00   63.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -77.0000   90.0000 94

  4 omega   20.00  104.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000 -180.0000 84

  5 omega    1.00   75.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000 -150.0000 74

  6 omega   38.00   91.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

  7 omega   40.00  135.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   30.0000 95

  8 omega   38.00   91.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 53

  9 omega   81.00  176.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 95

 10 omega   38.00   91.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 53

 11 omega   40.00  135.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  150.0000 95

 12 omega   57.00  150.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000   90.0000 93

 13 omega  -31.00   53.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000  -60.0000 84

 14 omega   17.00  105.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   38.0000   30.0000 88

 15 omega   10.00  104.00   1.0000    1.1800
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000   60.0000 94
;
_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      0.1623421000
_diffrn_orient_matrix_UB_12      -0.0494349000
_diffrn_orient_matrix_UB_13      0.0001945000
_diffrn_orient_matrix_UB_21      -0.0569040000
_diffrn_orient_matrix_UB_22      -0.0970720000
_diffrn_orient_matrix_UB_23      0.0529670000
_diffrn_orient_matrix_UB_31      -0.0381888000
_diffrn_orient_matrix_UB_32      -0.0665474000
_diffrn_orient_matrix_UB_33      -0.0775799000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9066
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         4.550
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.315
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42110
_exptl_absorpt_correction_type   multi-scan
_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)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.659
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Flack x determined using 1173 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.016(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         3091
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0995P)^2^+0.2319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1414
_refine_ls_wR_factor_ref         0.1445
_reflns_Friedel_coverage         0.729
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2928
_reflns_number_total             3091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc06481g2.cif
_cod_data_source_block           fxm-lyb
_cod_original_cell_volume        1730.45(13)
_cod_database_code               7125052
_reflns_odcompleteness_completeness 99.83
_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. Restrained distances
 C1-C00K
 1.29 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C00H(H00G,H00H), C00I(H00I,H00J)
3.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00D(H00D), C00K(H00N)
3.c X=CH2 refined with riding coordinates:
 C1(H1A,H1B)
3.d Idealised Me refined as rotating group:
 C00G(H00A,H00E,H00F), C00J(H00K,H00L,H00M), C00L(H00O,H00P,H00Q)
;
_shelx_res_checksum              71596
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-09-28
_olex2_submission_special_instructions 'No special instructions were received'