Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cycloaddition of 3-Acyloxy 1,4-Enyne and Alkene.
Shu, Xing-zhong; Schienebeck, Casi M.; Li, Xiaoxun; Zhou, Xin; Song, Wangze; Chen, Lianqing; Guzei, Ilia A.; Tang, Weiping; Organic letters 17 (2015) 5128–5131; doi:10.1021/acs.orglett.5b02665

data_1555365
_publ_section_title
;
 Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cycloaddition of
 3-Acyloxy 1,4-Enyne and Alkene.
;
_journal_issue                   20
_journal_name_full               'Organic letters'
_journal_page_first              5128
_journal_page_last               5131
_journal_paper_doi               10.1021/acs.orglett.5b02665
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H25 Br N2 O4 S'
_chemical_formula_sum            'C24 H25 Br N2 O4 S'
_chemical_formula_weight         517.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-05-07
_audit_creation_method
;
  Olex2 1.2-dev
  (compiled Apr 23 2013 16:52:19, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.810(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.512(4)
_cell_length_b                   19.054(7)
_cell_length_c                   30.838(14)
_cell_measurement_reflns_used    9956
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.69
_cell_measurement_theta_min      2.24
_cell_volume                     5577(4)
_computing_cell_refinement       'SAINT+ Ver. 8.30C (Bruker-AXS, 2013)'
_computing_data_collection       'APEX2 Ver. 2013.2-0 (Bruker-AXS, 2013)'
_computing_data_reduction        'SAINT+ Ver. 8.30C (Bruker-AXS, 2013)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            57938
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.340
_diffrn_reflns_theta_min         1.324
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.577
_exptl_absorpt_correction_T_max  0.5334
_exptl_absorpt_correction_T_min  0.4668
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0949 before and 0.0460 after correction.
The Ratio of minimum to maximum transmission is 0.8751.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.722
_refine_diff_density_min         -0.450
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.043(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    const
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         13840
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0649P)^2^+8.4904P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1229
_refine_ls_wR_factor_ref         0.1259
_reflns_Friedel_coverage         0.943
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                12299
_reflns_number_total             13840
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02665_si_002.cif
_cod_data_source_block           tang17a_sq_s
_cod_database_code               1555365
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uiso(C8A) = Uiso(C14A) = Uiso(C8B) = Uiso(C14B) = Uiso(C9A) = Uiso(C10A) = Uiso(C12A) = Uiso(C13A) = Uiso(C12B) = Uiso(C13B) = Uiso(C10B) = Uiso(C9B)
3. Same fragment restrains
{S1A, O3A, N1A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A}
{S1A, O3A, N1A, C7A, C8B, C9B, C10B, C11A, C12B, C13B, C14B, C15A}
as
{S1, O3, N1, C7, C8, C9, C10, C11, C12, C13, C14, C15}
4. Others
 Sof(H7AC)=Sof(H7AD)=Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(C10B)=
 Sof(H10B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=Sof(H13B)=Sof(C14B)=Sof(H14B)=
 Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(H7AA)=Sof(H7AB)=Sof(H15A)=Sof(H15B)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9AA)=
 Sof(H9AB)=Sof(C10A)=Sof(H10A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=
 Sof(C14A)=Sof(H14A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C14(H14), C8B(H8B), C14B(H14B), C8A(H8A), C14A(H14A)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C15(H15E,H15F), C7A(H7AC,H7AD), C7A(H7AA,H7AB),
 C9B(H9BA,H9BB), C15A(H15C,H15D), C15A(H15A,H15B), C9A(H9AA,H9AB)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C12(H12), C13(H13), C2(H2), C3(H3), C5(H5), C6(H6), C18(H18),
 C19(H19), C21(H21), C22(H22), C10B(H10B), C12B(H12B), C13B(H13B), C2A(H2A),
 C3A(H3A), C5A(H5A), C6A(H6A), C10A(H10A), C12A(H12A), C13A(H13A), C18A(H18A),
 C19A(H19A), C21A(H21A), C22A(H22A)
5.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C17(C18,C19,C20,C21,C22), C1A(C2A,C3A,C4A,C5A,C6A),
 C17A(C18A,C19A,C20A,C21A,C22A)
5.e Idealised Me refined as rotating group:
 C23(H23D,H23E,H23F), C24(H24D,H24E,H24F), C23A(H23A,H23B,H23C), C24A(H24A,
 H24B,H24C)
;
_shelx_estimated_absorpt_t_max   0.858
_shelx_estimated_absorpt_t_min   0.571
_shelx_fab_checksum              40418
_shelx_hkl_checksum              13318
_shelx_res_checksum              91287
_shelxl_version_number           2013-3