Synthesis of Complex Hexacyclic Compounds via a Tandem Rh(II)-Catalyzed Double-Cyclopropanation/Cope Rearrangement/Diels-Alder Reaction.
Spangler, Jillian E.; Lian, Yajing; Raikar, Sandeep N.; Davies, Huw M. L.; Organic letters 16 (2014) 4794–4797; doi:10.1021/ol502257d

data_1517905
_publ_section_title
;
 Synthesis of Complex Hexacyclic Compounds via a Tandem Rh(II)-Catalyzed
 Double-Cyclopropanation/Cope Rearrangement/Diels-Alder Reaction.
;
_journal_issue                   18
_journal_name_full               'Organic letters'
_journal_page_first              4794
_journal_page_last               4797
_journal_paper_doi               10.1021/ol502257d
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H34 O3 Si'
_chemical_formula_sum            'C27 H34 O3 Si'
_chemical_formula_weight         434.63
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-07-21
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.02340(10)
_cell_length_b                   10.8338(3)
_cell_length_c                   37.8963(8)
_cell_measurement_reflns_used    8849
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      25.677
_cell_measurement_theta_min      2.477
_cell_volume                     2472.97(10)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0654
_diffrn_reflns_av_unetI/netI     0.0554
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            23362
_diffrn_reflns_theta_full        25.74
_diffrn_reflns_theta_max         25.74
_diffrn_reflns_theta_min         1.07
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.120
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5586
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0840 before and 0.0634 after correction. The Ratio of minimum to maximum transmission is 0.7495. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.167
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             936
_exptl_crystal_recrystallization_method
'The material was recrystallised from pentane by slow evaporation'
_exptl_crystal_size_max          0.369
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.092
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.07(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         4724
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0562
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0463P)^2^+0.3067P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.0985
_reflns_number_gt                3997
_reflns_number_total             4724
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol502257d_si_003.cif
_cod_data_source_block           jesi033
_cod_database_code               1517905
_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 Ternary CH refined with riding coordinates:
 C5(H5), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C21(H21)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'