New Initiation Modes for Directed Carbonylative C-C Bond Activation: Rhodium-Catalyzed (3 + 1 + 2) Cycloadditions of Aminomethylcyclopropanes.
Wang, Gang-Wei; McCreanor, Niall G.; Shaw, Megan H.; Whittingham, William G.; Bower, John F.; Journal of the American Chemical Society 138 (2016) 13501–13504; doi:10.1021/jacs.6b08608

data_4130989
_publ_section_title
;
 New Initiation Modes for Directed Carbonylative C-C Bond Activation:
 Rhodium-Catalyzed (3 + 1 + 2) Cycloadditions of Aminomethylcyclopropanes.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13501
_journal_page_last               13504
_journal_paper_doi               10.1021/jacs.6b08608
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C15 H19 N O3 S'
_chemical_formula_sum            'C15 H19 N O3 S'
_chemical_formula_weight         293.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-09-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.98(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6249(17)
_cell_length_b                   14.820(3)
_cell_length_c                   10.971(2)
_cell_measurement_reflns_used    5555
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      29.50
_cell_measurement_theta_min      2.84
_cell_volume                     1394.7(5)
_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
;
XL, 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      173.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.972
_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  0.0233
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            59580
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         33.112
_diffrn_reflns_theta_min         1.866
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.239
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6459
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0705 before and 0.0430 after correction.
The Ratio of minimum to maximum transmission is 0.8659.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       Plate
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.56(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     410
_refine_ls_number_reflns         10077
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0310
_refine_ls_R_factor_gt           0.0296
_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^)+(0.0478P)^2^+0.1924P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0788
_reflns_Friedel_coverage         0.937
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                9780
_reflns_number_total             10077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08608_si_002.cif
_cod_data_source_block           nmc04000
_cod_database_code               4130989
_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. Rigid bond restraints
 N2, C29B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C9A) = Uanis(C9B) = Uanis(C14A) = Uanis(C14B)
4. Others
 Sof(H8BC)=Sof(H8BD)=Sof(C9B)=Sof(H9B)=Sof(C33B)=Sof(H33A)=Sof(H33B)=Sof(C30B)=
 Sof(H30A)=Sof(H30B)=Sof(H13C)=Sof(H13D)=Sof(C14B)=Sof(H14B)=Sof(H15C)=
 Sof(H15D)=Sof(H28C)=Sof(H28D)=Sof(C29B)=Sof(H29B)=Sof(H31C)=Sof(H31D)=
 Sof(C34B)=Sof(H34B)=Sof(H35C)=Sof(H35D)=Sof(H11C)=Sof(H11D)=Sof(C10B)=
 Sof(H10C)=Sof(H10D)=1-FVAR(1)
 Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H13A)=
 Sof(H13B)=Sof(C14A)=Sof(H14A)=Sof(H15A)=Sof(H15B)=Sof(H28A)=Sof(H28B)=
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(H31A)=Sof(H31B)=
 Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34A)=Sof(H35A)=Sof(H35B)=
 Sof(H11A)=Sof(H11B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C9A(H9A), C9B(H9B), C14A(H14A), C14B(H14B), C29A(H29A), C29B(H29B),
 C34A(H34A), C34B(H34B)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8AA,H8AB), C8(H8BC,H8BD), C10A(H10A,H10B), C33B(H33A,H33B), C30B(H30A,
 H30B), C13(H13A,H13B), C13(H13C,H13D), C15(H15A,H15B), C15(H15C,H15D),
 C28(H28A,H28B), C28(H28C,H28D), C30A(H30C,H30D), C31(H31C,H31D), C31(H31A,
 H31B), C33A(H33C,H33D), C35(H35A,H35B), C35(H35C,H35D), C11(H11A,H11B),
 C11(H11C,H11D), C10B(H10C,H10D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C22(H22), C23(H23), C25(H25), C26(H26)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C27(H27A,H27B,H27C)
;
_shelx_hkl_checksum              20391
_shelx_res_checksum              68683
_shelxl_version_number           2013-3