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_4123204
_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         'C32 H22 F18 N O5 P Rh, C F3 O3 S, C7 H8'
_chemical_formula_sum            'C40 H30 F21 N O8 P Rh S'
_chemical_formula_weight         1217.59
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-06-11
_audit_creation_method
;
Olex2 1.2
(compiled 2014.05.21 svn.r2940 for OlexSys, GUI svn.r4846)
;
_cell_angle_alpha                96.097(4)
_cell_angle_beta                 93.726(5)
_cell_angle_gamma                113.041(5)
_cell_formula_units_Z            2
_cell_length_a                   11.9218(14)
_cell_length_b                   12.1401(14)
_cell_length_c                   17.385(2)
_cell_measurement_reflns_used    9896
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      66.91
_cell_measurement_theta_min      2.57
_cell_volume                     2286.7(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker Pt135 CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.941
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_device       'Bruker Mircostar Rotating anode'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0561
_diffrn_reflns_av_unetI/netI     0.0685
_diffrn_reflns_Laue_measured_fraction_full 0.941
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            19012
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.948
_diffrn_reflns_theta_min         2.573
_diffrn_source                   'micro-focus rotating anode'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.058
_exptl_absorpt_correction_T_max  0.3506
_exptl_absorpt_correction_T_min  0.0867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1265 before and 0.0782 after correction.
The Ratio of minimum to maximum transmission is 0.2473.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.768
_exptl_crystal_description       needle
_exptl_crystal_F_000             1212
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.175
_refine_diff_density_max         2.638
_refine_diff_density_min         -2.384
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     747
_refine_ls_number_reflns         7795
_refine_ls_number_restraints     345
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0637
_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^)+(0.1391P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1697
_refine_ls_wR_factor_ref         0.1760
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6836
_reflns_number_total             7795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja511335v_si_008.cif
_cod_data_source_block           testt2
_cod_depositor_comments
'Adding full bibliography for 4123199--4123207.cif.'
_cod_database_code               4123204
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.471
_shelx_estimated_absorpt_t_min   0.274
_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, All O(H,H) groups
2. Restrained distances
 F18B-C31 \\sim F18A-C31 \\sim F17B-C31 \\sim F17A-C31 \\sim F16B-C31 \\sim
F16A-C31
 with sigma of 0.005
 F13B-C30 \\sim F13C-C30 \\sim F14A-C30 \\sim F14B-C30 \\sim F14C-C30 \\sim
F15A-C30 \\sim F15B-C30 ~
 F15C-C30 \\sim F13A-C30
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F14A \\sim F14B \\sim F14C \\sim F15A \\sim F15B \\sim F15C \\sim F13A \\sim
F13B \\sim F13C: within 1.7A with sigma of 0.003 and sigma for terminal atoms
of 0.006
C33 \\sim C38 \\sim C37 \\sim C36 \\sim C35 \\sim C34 \\sim C39 \\sim C39A
\\sim C33A \\sim C34A \\sim C35A \\sim C36A \\sim C37A \\sim C38A: within 1.7A
with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F16B) \\sim Ueq, Uanis(F16A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(F18A) = Uanis(F18B)
Uanis(F17A) = Uanis(F17B)
Uanis(F16B) = Uanis(F16A)
Uanis(C38) = Uanis(C38A)
Uanis(C34A) = Uanis(C35)
Uanis(C36) = Uanis(C35A)
4. Others
 Fixed Sof: F18B(0.5699) F16B(0.5699) F17B(0.5699) F14B(0.44) F13B(0.44)
 F15C(0.44) C33(0.69316) C38(0.69316) H38(0.69316) C37(0.69316) H37(0.69316)
 C36(0.69316) H36(0.69316) C35(0.69316) H35(0.69316) C34(0.69316) H34(0.69316)
 C39(0.69316) H39A(0.69316) H39B(0.69316) H39C(0.69316) F17A(0.4301)
 F16A(0.4301) F18A(0.4301) F14A(0.28) F15A(0.28) F13A(0.28) F14C(0.28)
 F15B(0.28) F13C(0.28) C39A(0.30684) H39D(0.30684) H39E(0.30684) H39F(0.30684)
 C33A(0.30684) C34A(0.30684) H34A(0.30684) C35A(0.30684) H35A(0.30684)
 C36A(0.30684) H36A(0.30684) C37A(0.30684) H37A(0.30684) C38A(0.30684)
 H38A(0.30684)
5.a Rotating group:
 O4(H4A,H4B)
5.b Ternary CH refined with riding coordinates:
 C4(H4)
5.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2(H2A,H2B)
5.d Aromatic/amide H refined with riding coordinates:
 C21(H21), C11(H11), C9(H9), C25(H25), C13(H13), C27(H27), C17(H17), C29(H29),
 C19(H19), C38(H38), C37(H37), C36(H36), C35(H35), C34(H34), C34A(H34A),
 C35A(H35A), C36A(H36A), C37A(H37A), C38A(H38A)
5.e Fitted hexagon refined as free rotating group:
 C33(C38,C37,C36,C35,C34), C33A(C34A,C35A,C36A,C37A,C38A)
5.f Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C39(H39A,H39B,H39C), C39A(H39D,H39E,H39F)
;
_shelx_res_checksum              84013
_shelx_hkl_checksum              51440
_olex2_submission_special_instructions 'No special instructions were received'