Stereoselective synthesis of chiral sulfilimines from N-mesyloxycarbamates: metal-nitrenes versus metal-nitrenoids species.
Lebel, Hélène; Piras, Henri; The Journal of organic chemistry 80 (2015) 3572–3585; doi:10.1021/acs.joc.5b00256

data_4036148
_publ_section_title
;
 Stereoselective synthesis of chiral sulfilimines from
 N-mesyloxycarbamates: metal-nitrenes versus metal-nitrenoids species.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3572
_journal_page_last               3585
_journal_paper_doi               10.1021/acs.joc.5b00256
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C86 H84 N8 O16 Rh2'
_chemical_formula_sum            'C86 H84 N8 O16 Rh2'
_chemical_formula_weight         1691.43
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-10-29
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.4936(3)
_cell_length_b                   22.4947(3)
_cell_length_c                   23.0451(3)
_cell_measurement_reflns_used    9340
_cell_measurement_temperature    100
_cell_measurement_theta_max      71.684
_cell_measurement_theta_min      2.745
_cell_volume                     9068.6(2)
_computing_cell_refinement
;
SAINT (2013) V8.30C; Integration Software for Single Crystal Data.
Bruker AXS Inc., Madison, WI 53719-1173.
;
_computing_data_collection
;
APEX 2 (2013) Bruker AXS Inc., Madison, WI 53719-1173.
;
_computing_data_reduction
'SAINT (2013) V8.30C; Integration Software for Single Crystal Data. Bruker AXS Inc., Madison, WI 53719-1173.'
_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
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.3
_diffrn_detector_type            'Bruker APEX2 CCD'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker Smart APEX'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_collimation    'Focusing mirrors'
_diffrn_radiation_monochromator  'Quazar MX Mirror Optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            159688
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.75
_diffrn_reflns_theta_min         1.92
_diffrn_source                   'Microfocus Source'
_diffrn_source_target            Cu
_diffrn_source_type              'Incoatec I\mS High Brilliance Microsource'
_exptl_absorpt_coefficient_mu    3.468
_exptl_absorpt_correction_T_max  0.7535
_exptl_absorpt_correction_T_min  0.6516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0933 before and 0.0733 after correction.
The Ratio of minimum to maximum transmission is 0.8648.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            ' pink'
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.239
_exptl_crystal_description       FRAGMENT
_exptl_crystal_F_000             3496
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.496
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 7168 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.012(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1074
_refine_ls_number_reflns         17632
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0544P)^2^+3.3396P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.834
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                16415
_reflns_number_total             17632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00256_si_003.cif
_cod_data_source_block           hele56
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/saulius/struct/COD-crude-data/automatic-downloads/DataCite-retrospective/ACS/depositions/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4036148
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.769
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1-C2A \\sim C1-C2B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2A) = Uanis(C2B)
Uanis(N1A) = Uanis(N1B)
Uanis(C7A) = Uanis(C7B)
Uanis(C8A) = Uanis(C8B)
Uanis(C9A) = Uanis(C9B)
Uanis(C10A) = Uanis(C10B)
Uanis(C11A) = Uanis(C11B)
Uanis(C12A) = Uanis(C12B)
Uanis(C13A) = Uanis(C13B)
Uanis(C14A) = Uanis(C14B)
Uanis(C15A) = Uanis(C15B)
Uanis(C16A) = Uanis(C16B)
Uanis(C17A) = Uanis(C17B)
Uanis(C18A) = Uanis(C18B)
Uanis(O7A) = Uanis(O7B)
Uanis(O17A) = Uanis(O17B)
4. Same fragment restrains
{C2A, N1A, O7A, O17A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A, C16A,
C17A, C18A}
as
{C2B, N1B, O7B, O17B, C7B, C8B, C9B, C10B, C11B, C12B, C13B, C14B, C15B, C16B,
C17B, C18B}
5. Others
 Sof(C2B)=Sof(H2B)=Sof(N1B)=Sof(O7B)=Sof(O17B)=Sof(C7B)=Sof(C8B)=Sof(C9B)=
 Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(C13B)=Sof(H13B)=
 Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(C17B)=Sof(C18B)=1-FVAR(1)
 Sof(C2A)=Sof(H2A)=Sof(N1A)=Sof(O7A)=Sof(O17A)=Sof(C7A)=Sof(C8A)=Sof(C9A)=
 Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(C13A)=Sof(H13A)=
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(C17A)=Sof(C18A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C2A(H2A), C2B(H2B), C22(H22), C42(H42), C62(H62)
6.b Aromatic/amide H refined with riding coordinates:
 C9A(H9A), C10A(H10A), C11A(H11A), C13A(H13A), C14A(H14A), C15A(H15A),
 C9B(H9B), C10B(H10B), C11B(H11B), C13B(H13B), C14B(H14B), C15B(H15B), C29(H29),
  C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C49(H49), C50(H50),
 C51(H51), C53(H53), C54(H54), C55(H55), C69(H69), C70(H70), C71(H71), C73(H73),
  C74(H74), C75(H75), C81(H81), C82(H82), C84(H84), C85(H85), C91(H91),
 C92(H92), C94(H94), C95(H95)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C96(H96A,H96B,H96C),
 C97(H97A,H97B,H97C)
;