Enantioselective Synthesis of Chiral Medium-Sized Cyclic Compounds via Tandem Cycloaddition/Cope Rearrangement Strategy
Gao, Xing; Xia, Miaoren; Yuan, Chunhao; Zhou, Leijie; Sun, Wei; Li, Cheng; Wu, Bo; Zhu, Dongyu; Zhang, Cheng; Zheng, Bing; Wang, Dongqi; Guo, Hongchao; ACS Catalysis 9 (2019) 1645–; doi:10.1021/acscatal.8b04590

data_4514881
_publ_section_title
;
 Enantioselective Synthesis of Chiral Medium-Sized Cyclic Compounds via
 Tandem Cycloaddition/Cope Rearrangement Strategy
;
_journal_issue                   3
_journal_name_full               'ACS Catalysis'
_journal_page_first              1645
_journal_paper_doi               10.1021/acscatal.8b04590
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C17 H16 Br2 O5'
_chemical_formula_sum            'C17 H16 Br2 O5'
_chemical_formula_weight         460.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-11-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 114.021(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.6470(6)
_cell_length_b                   10.3884(2)
_cell_length_c                   17.2385(5)
_cell_measurement_reflns_used    11877
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      72.9190
_cell_measurement_theta_min      2.3990
_cell_volume                     3377.26(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14e (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.941
_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    -53.00 -27.00   0.50    1.20    --  -47.32 106.00  76.00   52
  2  \w      4.00  85.00   0.50    1.20    --   47.32-106.00 -22.00  162
  3  \w   -165.00 -94.00   0.50    1.50    --  -99.00-106.00 -22.00  142
  4  \w    -89.00 -64.00   0.50    1.50    --  -99.00 106.00  76.00   50
  5  \w     96.00 169.00   0.50    1.50    --  103.25 106.00  76.00  146
  6  \w     68.00 101.00   0.50    1.50    --  103.25-106.00 -22.00   66
  7  \w   -107.00 -75.00   0.50    1.20    --  -47.32-125.00  90.00   64
  8  \w   -119.00 -74.00   0.50    1.20    --  -47.32-125.00  60.00   90
  9  \w   -116.00 -87.00   0.50    1.20    --  -47.32-125.00 120.00   58
 10  \w     29.00 119.00   0.50    1.20    --   47.32  77.00  60.00  180
 11  \w    -89.00 -49.00   0.50    1.50    --  -99.00  77.00  90.00   80
 12  \w   -107.00 -26.00   0.50    1.50    --  -99.00  30.00  90.00  162
 13  \w   -112.00 -28.00   0.50    1.50    --  -99.00  45.00 -60.00  168
 14  \w   -168.00-137.00   0.50    1.50    --  -99.00 -45.00   0.00   62
 15  \w   -147.00 -85.00   0.50    1.50    --  -99.00 -15.00  30.00  124
 16  \w   -132.00-106.00   0.50    1.50    --  -99.00 -45.00   0.00   52
 17  \w     59.00 108.00   0.50    1.50    --  103.25 -94.00   0.00   98
 18  \w    100.00 138.00   0.50    1.50    --  103.25  15.00-180.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0357903000
_diffrn_orient_matrix_UB_12      0.1283882000
_diffrn_orient_matrix_UB_13      0.0390010000
_diffrn_orient_matrix_UB_21      -0.0733556000
_diffrn_orient_matrix_UB_22      0.0645035000
_diffrn_orient_matrix_UB_23      -0.0295738000
_diffrn_orient_matrix_UB_31      -0.0038311000
_diffrn_orient_matrix_UB_32      -0.0367679000
_diffrn_orient_matrix_UB_33      0.0846121000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21309
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.811
_diffrn_reflns_theta_min         2.343
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.315
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74555
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.810
_exptl_crystal_description       prism
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.890
_refine_diff_density_min         -0.955
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     472
_refine_ls_number_reflns         6597
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0625
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0953P)^2^+4.3538P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1519
_refine_ls_wR_factor_ref         0.1666
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5447
_reflns_number_total             6597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04590_si_006.cif
_cod_data_source_block           tx73
_cod_original_cell_volume        3377.26(18)
_cod_database_code               4514881
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHOBr
_reflns_odcompleteness_completeness 99.91
_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
 Br0A-C24
 1.94 with sigma of 0.01
 Br4-C24 = Br1-C1 = Br1A-C1 = Br2A-C4 = Br2-C4
 1.94 with sigma of 0.01
 Br3-C18 = Br-C18
 1.94 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Br1 \\sim Br2 \\sim Br3 \\sim Br4 \\sim Br \\sim Br0A \\sim Br1A \\sim Br2A:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(Br4) \\sim Ueq, Uanis(Br0A) \\sim Ueq, Uanis(Br1) \\sim Ueq, Uanis(Br1A)
\\sim Ueq, Uanis(Br2) \\sim Ueq, Uanis(Br2A) \\sim Ueq, Uanis(Br3) \\sim Ueq,
Uanis(Br) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H11A)=Sof(H9B)=Sof(H33A)=Sof(H34A)=Sof(Br)=Sof(Br0A)=Sof(Br1A)=Sof(Br2A)=
 1-FVAR(1)
 Sof(H1)=Sof(H4)=Sof(Br1)=Sof(Br2)=Sof(H18)=Sof(H24)=Sof(Br3)=Sof(Br4)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C1(H11A), C3(H3), C4(H4), C4(H9B), C8(H8), C18(H18), C18(H33A),
 C20(H20), C22(H22), C24(H24), C24(H34A)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C23(H23A,H23B), C26(H26A,H26B)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C28(H28), C29(H29),
 C30(H30), C31(H31), C32(H32)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C34(H2,H34B,H34C)
;
_shelx_res_checksum              36787
_shelx_hkl_checksum              10005
_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 2.150
_oxdiff_exptl_absorpt_empirical_full_min 0.483