Phosphine-Catalyzed Regiodivergent Annulations of γ-Substituted Allenoates with Conjugated Dienes
Gan, Zhenjie; Gong, Yanchuan; Chu, Yunpeng; Li, Erqing; Huang, You; duan, zheng; Chemical Communications  (2019) –; doi:10.1039/C9CC05207K

data_7123928
_publ_section_title
;
 Phosphine-Catalyzed Regiodivergent Annulations of \g-Substituted
 Allenoates with Conjugated Dienes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC05207K
_journal_year                    2019
_chemical_formula_moiety         'C22 H25 Br O6'
_chemical_formula_sum            'C22 H25 Br O6'
_chemical_formula_weight         465.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-23 deposited with the CCDC.    2019-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.534(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.04519(13)
_cell_length_b                   20.9360(4)
_cell_length_c                   18.0511(4)
_cell_measurement_reflns_used    3250
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6920
_cell_measurement_theta_min      4.2140
_cell_volume                     2259.29(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    '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 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -14.00   37.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000 -180.0000 102

  2 omega -100.00  -21.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   60.0000 158

  3 omega   32.00   66.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -120.0000 68

  4 omega   58.00  110.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -120.0000 104

  5 omega   59.00  105.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   30.0000 92

  6 omega   -1.00   60.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000  -60.0000 122

  7 omega   72.00  105.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000  -60.0000 66

  8 omega   78.00  104.00   0.5000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000    0.0000 52

  9 omega  140.00  174.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 68

 10 omega   40.00   67.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 54

 11 omega   93.00  119.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 52

 12 omega   78.00  104.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 52

 13 omega   38.00  100.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  150.0000 124

 14 omega   92.00  175.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   60.0000 166

 15 omega  116.00  150.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 68

 16 omega   38.00   85.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 94

 17 omega   41.00   67.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  150.0000 52

 18 omega   44.00   89.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 90

 19 omega  110.00  176.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 132

 20 omega   64.00  136.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -120.0000 144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0436026000
_diffrn_orient_matrix_UB_12      0.0689908000
_diffrn_orient_matrix_UB_13      -0.0279806000
_diffrn_orient_matrix_UB_21      0.0056198000
_diffrn_orient_matrix_UB_22      0.0228913000
_diffrn_orient_matrix_UB_23      0.0813615000
_diffrn_orient_matrix_UB_31      0.2540098000
_diffrn_orient_matrix_UB_32      0.0114060000
_diffrn_orient_matrix_UB_33      0.0063893000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            8982
_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         4.223
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.765
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84928
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_description       prism
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.033
_refine_diff_density_min         -0.678
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4030
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0708
_refine_ls_R_factor_gt           0.0588
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0925P)^2^+1.3013P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1584
_refine_ls_wR_factor_ref         0.1732
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3303
_reflns_number_total             4030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc05207k2.cif
_cod_data_source_block           20190496
_cod_original_cell_volume        2259.30(8)
_cod_database_code               7123928
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4Br1
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.622
_reflns_odcompleteness_completeness 99.93
_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
 C21A-C22A
 1.53 with sigma of 0.02
 C21-C22
 1.53 with sigma of 0.02
 C18-C19
 1.53 with sigma of 0.02
 C19A-C18A
 1.53 with sigma of 0.02
 O6A-C21A
 1.45 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19A) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C22A) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C18) = Uanis(C18A)
Uanis(C19) = Uanis(C19A)
Uanis(C21) = Uanis(C21A)
Uanis(C22) = Uanis(C22A)
Uanis(O4) = Uanis(O4A)
Uanis(O3) = Uanis(O3A)
Uanis(O5) = Uanis(O5A)
Uanis(O6) = Uanis(O6A)
4. Others
 Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=
 Sof(O3A)=Sof(O4A)=1-FVAR(1)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(O3)=
 Sof(O4)=FVAR(1)
 Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=
 Sof(O5A)=Sof(O6A)=1-FVAR(2)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(O5)=
 Sof(O6)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C18(H18A,H18B), C18A(H18C,H18D), C21(H21A,H21B), C21A(H21C,
 H21D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C8(H8), C13(H13), C14(H14)
5.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F), C22(H22A,H22B,
 H22C), C22A(H22D,H22E,H22F)
;
_olex2_submission_special_instructions 'No special instructions were received'