Formaldehyde N,N-dialkylhydrazones as neutral formyl anion equivalents in iridium-catalyzed asymmetric allylic substitution.
Breitler, Simon; Carreira, Erick M.; Journal of the American Chemical Society 137 (2015) 5296–5299; doi:10.1021/jacs.5b01951

data_4129406
_publ_section_title
;
 Formaldehyde N,N-dialkylhydrazones as neutral formyl anion equivalents in
 iridium-catalyzed asymmetric allylic substitution.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5296
_journal_page_last               5299
_journal_paper_doi               10.1021/jacs.5b01951
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C19 H25 F3 N2 O2'
_chemical_formula_sum            'C19 H25 F3 N2 O2'
_chemical_formula_weight         370.41
_chemical_name_systematic
2,2,2-trifluoro-N-((S)-2-(methoxymethyl)pyrrolidin-1-yl)-N-((2R,3R)-3-phenylpent-4-en-2-yl)acetamide
_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     iterative
_audit_creation_date             2014-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.2312(5)
_cell_length_b                   12.0232(7)
_cell_length_c                   18.8874(12)
_cell_measurement_reflns_used    9887
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      27.54
_cell_measurement_theta_min      2.74
_cell_volume                     1869.2(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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., 2015)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'focusing graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0144
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            29343
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.540
_diffrn_reflns_theta_min         2.008
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.105
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7258
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0350 before and 0.0310 after correction.
The Ratio of minimum to maximum transmission is 0.9734.
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    1.316
_exptl_crystal_description       plank
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1709 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         4247
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0261
_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^)+(0.0351P)^2^+0.3582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0646
_refine_ls_wR_factor_ref         0.0661
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                4037
_reflns_number_total             4247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01951_si_003.cif
_cod_data_source_block           mo_ca121214_1_1_0m
_cod_database_code               4129406
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.959
_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.a Ternary CH refined with riding coordinates:
 C10(H10), C11(H11), C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C22(H22A,H22B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C12(H12), C15(H15), C16(H16), C17(H17), C21(H21)
2.d X=CH2 refined with riding coordinates:
 C26(H26A,H26B)
2.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              61325
_shelx_hkl_checksum              11734
_olex2_date_sample_data_collection 18.12.2014
_olex2_date_sample_submission    15.12.2014
_olex2_submission_special_instructions 'No special instructions were received'