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_1517904
_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_formula_moiety         'C46 H42 O5'
_chemical_formula_sum            'C46 H42 O5'
_chemical_formula_weight         674.79
_chemical_name_systematic
;
 ?
;
_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
_audit_creation_date             2014-06-13
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.05.21 svn.r2940 for OlexSys, GUI svn.r4846)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4278(8)
_cell_length_b                   20.659(3)
_cell_length_c                   26.404(3)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      62.467
_cell_measurement_theta_min      2.714
_cell_volume                     3506.2(8)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.891
_diffrn_measured_fraction_theta_max 0.947
_diffrn_measurement_device_type  'Bruker APEX-II CCD Cu'
_diffrn_measurement_method       '\w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0187
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_Laue_measured_fraction_full 0.891
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            15235
_diffrn_reflns_point_group_measured_fraction_full 0.856
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        65.000
_diffrn_reflns_theta_max         62.495
_diffrn_reflns_theta_min         2.716
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.648
_exptl_absorpt_correction_T_max  0.7522
_exptl_absorpt_correction_T_min  0.6909
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0911 before and 0.0314 after correction.
The Ratio of minimum to maximum transmission is 0.9185.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       plate
_exptl_crystal_F_000             1432
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of diethyl ether and hexane by slow evaporation'
_exptl_crystal_size_max          0.729
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.132
_refine_diff_density_max         0.118
_refine_diff_density_min         -0.138
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 1895 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.01(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         5116
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0300
_refine_ls_R_factor_gt           0.0277
_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^)+(0.0359P)^2^+0.4739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0660
_refine_ls_wR_factor_ref         0.0679
_reflns_Friedel_coverage         0.672
_reflns_Friedel_fraction_full    0.808
_reflns_Friedel_fraction_max     0.864
_reflns_number_gt                4844
_reflns_number_total             5116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol502257d_si_002.cif
_cod_data_source_block           jes5-135-01
_cod_original_cell_volume        3506.3(8)
_cod_database_code               1517904
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.649
_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
 C41A-C38 \\sim C41B-C38
 with sigma of 0.003
3. Uiso/Uaniso restraints and constraints
Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C44A) = Uanis(C42A)
Uanis(C41A) = Uanis(C41B)
Uanis(C43A) = Uanis(C43B)
Uanis(C1A) = Uanis(C1B)
Uanis(C46A) = Uanis(C46B)
Uanis(C42A) = Uanis(C45A)
Uanis(C45A) = Uanis(C45B)
Uanis(C44B) = Uanis(C44A)
Uanis(C42A) = Uanis(C42B)
4. Rigid body (RIGU) restrains
 C41A, C46A, C45A, C44A, C43A, C42A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Others
 Sof(C41B)=Sof(C46B)=Sof(H46B)=Sof(C45B)=Sof(H45B)=Sof(C44B)=Sof(H44B)=
 Sof(C43B)=Sof(H43B)=Sof(C42B)=Sof(H42B)=1-FVAR(1)
 Sof(C41A)=Sof(C46A)=Sof(H46A)=Sof(C45A)=Sof(H45A)=Sof(C44A)=Sof(H44A)=
 Sof(C43A)=Sof(H43A)=Sof(C42A)=Sof(H42A)=FVAR(1)
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=1-FVAR(2)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C23(H23), C16(H16), C21(H21), C30(H30), C22(H22), C20(H20)
6.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C29(H29A,H29B), C28(H28A,H28B)
6.c Aromatic/amide H refined with riding coordinates:
 C31(H31), C5(H5), C6(H6), C36(H36), C9(H9), C8(H8), C12(H12), C37(H37),
 C46A(H46A), C45A(H45A), C44A(H44A), C43A(H43A), C42A(H42A), C13(H13), C40(H40),
  C15(H15), C11(H11), C14(H14), C39(H39), C46B(H46B), C45B(H45B), C44B(H44B),
 C43B(H43B), C42B(H42B)
6.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C19(H19A,H19B,H19C), C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,
 H1BC)
;
_shelx_res_checksum              74816
_shelx_hkl_checksum              5060
_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'