TfNH2 as Achiral Hydrogen-Bond Donor Additive to Enhance the Selectivity of a Transition Metal Catalyzed Reaction. Highly Enantio- and Diastereoselective Rhodium-Catalyzed Cyclopropanation of Alkenes Using α-Cyano Diazoacetamide
David Marcoux; Soula Azzi; André B. Charette; Journal of the American Chemical Society 131 (2009) 6970–6972; doi:10.1021/ja902205f

data_4104419
_publ_section_title
;
 TfNH2 as Achiral Hydrogen-Bond Donor Additive to Enhance the Selectivity
 of a Transition Metal Catalyzed Reaction. Highly Enantio- and
 Diastereoselective Rhodium-Catalyzed Cyclopropanation of Alkenes Using
 \a-Cyano Diazoacetamide
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6970
_journal_page_last               6972
_journal_paper_doi               10.1021/ja902205f
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration rmad
_chemical_compound_source        'Synthesized by the authors. See text'
_chemical_formula_moiety         'C15 H15 Br N2 O'
_chemical_formula_sum            'C15 H15 Br N2 O'
_chemical_formula_weight         319.20
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.3066(7)
_cell_length_b                   8.1880(8)
_cell_length_c                   26.402(2)
_cell_measurement_reflns_used    18519
_cell_measurement_temperature    150
_cell_measurement_theta_max      68.26
_cell_measurement_theta_min      3.35
_cell_volume                     1363.4(2)
_computing_cell_refinement       'SAINT V7.34A (Bruker AXS, 2006b)'
_computing_data_collection       'APEX2 v2.1-0 (Bruker AXS, 2006a)'
_computing_data_reduction        'SAINT V7.34A (Bruker AXS, 2006b)'
_computing_molecular_graphics    'SHELXTL v6.12 (Bruker AXS, 2001)'
_computing_publication_material  'UdMX (Maris, 2004)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.927
_diffrn_measured_fraction_theta_max 0.927
_diffrn_measurement_device_type  'Bruker Microstar'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  'Helios optics'
_diffrn_radiation_source         'Rotating Anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.052
_diffrn_reflns_av_sigmaI/netI    0.0192
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            21815
_diffrn_reflns_theta_full        68.28
_diffrn_reflns_theta_max         68.28
_diffrn_reflns_theta_min         3.35
_diffrn_standards_decay_%        3.70
_diffrn_standards_interval_time  900
_diffrn_standards_number         167
_exptl_absorpt_coefficient_mu    4.051
_exptl_absorpt_correction_T_max  0.8856
_exptl_absorpt_correction_T_min  0.5968
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sadabs (Sheldrick, 1996)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.555
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Chunk
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.601
_refine_diff_density_min         -0.278
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details 'Flack H D (1983), 813 Friedel Pairs'
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2300
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0347
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0624P)^2^+0.8182P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0938
_refine_ls_wR_factor_ref         0.0940
_reflns_number_gt                2278
_reflns_number_total             2300
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja902205f_si_002.cif
_cod_data_source_block           cha186
_cod_depositor_comments
;
The following automatic conversions were performed:

'_geom_bond_publ_flag' value 'Y' changed to 'y' according to the
built-in table from CIF Core dictionary named 'cif_core.dic' version
2.4.1 from 2010-06-29 (21 time).

'_geom_angle_publ_flag' value 'Y'
changed to 'y' according to the built-in table from CIF Core
dictionary named 'cif_core.dic' version 2.4.1 from 2010-06-29 (31
time).

'_geom_torsion_publ_flag' value 'Y' changed to 'y' according
to the built-in table from CIF Core dictionary named 'cif_core.dic'
version 2.4.1 from 2010-06-29 (43 times).

Automatic conversion script
Id: cif_fix_values 1715 2011-07-08 13:25:40Z adriana 
;
_cod_original_cell_volume        1363.3(2)
_cod_database_code               4104419