Reversible C-C bond activation enables stereocontrol in rh-catalyzed carbonylative cycloadditions of aminocyclopropanes.
Shaw, Megan H.; McCreanor, Niall G.; Whittingham, William G.; Bower, John F.; Journal of the American Chemical Society 137 (2015) 463–468; doi:10.1021/ja511335v

data_4123206
_publ_section_title
;
 Reversible C-C bond activation enables stereocontrol in rh-catalyzed
 carbonylative cycloadditions of aminocyclopropanes.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              463
_journal_page_last               468
_journal_paper_doi               10.1021/ja511335v
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C34 H22 F21 N O7 P Rh S'
_chemical_formula_sum            'C34 H22 F21 N O7 P Rh S'
_chemical_formula_weight         1121.46
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-05-08
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                89.2240(10)
_cell_angle_beta                 85.1560(10)
_cell_angle_gamma                76.9780(10)
_cell_formula_units_Z            2
_cell_length_a                   9.8425(2)
_cell_length_b                   11.6612(2)
_cell_length_c                   18.2368(4)
_cell_measurement_reflns_used    8448
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      26.64
_cell_measurement_theta_min      2.32
_cell_volume                     2031.99(7)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Bruker Apex II kappa CCDC area detector'
_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  0.0453
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            33202
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.819
_diffrn_reflns_theta_min         1.792
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.656
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0613 before and 0.0475 after correction.
The Ratio of minimum to maximum transmission is 0.8573.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.833
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.047
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         8687
_refine_ls_number_restraints     336
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0319P)^2^+3.0396P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0778
_refine_ls_wR_factor_ref         0.0846
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7083
_reflns_number_total             8687
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja511335v_si_009.cif
_cod_data_source_block           testt1
_cod_depositor_comments
'Adding full bibliography for 4123199--4123207.cif.'
_cod_database_code               4123206
_shelxl_version_number           2013-3
_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
 F21A-C34 \\sim F21-C34 \\sim F20A-C34 \\sim F20-C34 \\sim F19A-C34 \\sim
F19-C34
 with sigma of 0.01
 F10B-C25 \\sim F10A-C25 \\sim F10-C25 \\sim F11B-C25 \\sim F11A-C25 \\sim
F11-C25 \\sim F12B-C25 ~
 F12A-C25 \\sim F12-C25
 with sigma of 0.01
 F7A-C18 \\sim F7-C18 \\sim F2AA-C18 \\sim F8A-C18 \\sim F8-C18 \\sim F0AA-C18
\\sim F9A-C18 \\sim F9-C18
 \\sim F1AA-C18
 with sigma of 0.01
 F4-C17 \\sim F4A-C17 \\sim F5A-C17 \\sim F5-C17 \\sim F6A-C17 \\sim F6-C17
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F20A \\sim F20 \\sim F19A \\sim F19 \\sim F21A \\sim F21: within 1.7A with
sigma of 0.003 and sigma for terminal atoms of 0.006
F10B \\sim F10A \\sim F10 \\sim F11B \\sim F11A \\sim F11 \\sim F12B \\sim F12A
\\sim F12: within 1.7A with sigma of 0.003 and sigma for terminal atoms of 0.006
F9 \\sim F7 \\sim F8 \\sim F7A \\sim F9A \\sim F8A \\sim F0AA \\sim F1AA \\sim
F2AA: within 1.7A with sigma of 0.003 and sigma for terminal atoms of 0.006
F6 \\sim F5 \\sim F4 \\sim F6A \\sim F4A \\sim F5A: within 1.7A with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(F6) \\sim Ueq, Uanis(F6A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(F19) \\sim Ueq, Uanis(F19A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
4. Others
 Fixed Sof: F9(0.61) F7(0.61) F19(0.61933) F21(0.61933) F8(0.61) F6(0.58)
 F20(0.61933) F5(0.58) F4(0.58) F12A(0.47) F10A(0.47) F11A(0.47) F10B(0.35)
 F12B(0.35) F11B(0.35) F6A(0.42) F4A(0.42) F5A(0.42) F19A(0.38067)
 F20A(0.38067) F21A(0.38067) F12(0.18) F11(0.18) F10(0.18) F7A(0.16) F9A(0.16)
 F8A(0.16) F0AA(0.23) F1AA(0.23) F2AA(0.23)
5.a Ternary CH refined with riding coordinates:
 C5(H5)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C6(H6A,H6B), C2(H2A,H2B)
5.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C20(H20), C16(H16), C32(H32), C24(H24), C28(H28), C30(H30),
 C14(H14), C12(H12)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              91997
_shelx_hkl_checksum              81153