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_4129405
_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 ad
_chemical_formula_moiety         'C16 H16 S2'
_chemical_formula_sum            'C16 H16 S2'
_chemical_formula_weight         272.41
_chemical_melting_point          '84-86&#x00B0;C (hexane)'
_chemical_name_systematic        (R)-2-(-(naphtalen-2-yl)allyl)-1,3-dithiolane
_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             2014-12-08
_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                   5.59320(10)
_cell_length_b                   11.2720(2)
_cell_length_c                   22.6456(4)
_cell_measurement_reflns_used    7175
_cell_measurement_temperature    223.2(2)
_cell_measurement_theta_max      67.15
_cell_measurement_theta_min      3.90
_cell_volume                     1427.73(4)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      223.2(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 0.982
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            19292
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.272
_diffrn_reflns_theta_min         3.904
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.191
_exptl_absorpt_correction_T_max  0.7413
_exptl_absorpt_correction_T_min  0.6393
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0746 before and 0.0596 after correction.
The Ratio of minimum to maximum transmission is 0.8624.
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    1.267
_exptl_crystal_description       plate
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.115
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 947 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.038(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         2529
_refine_ls_number_restraints     219
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0337
_refine_ls_R_factor_gt           0.0313
_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^)+(0.0390P)^2^+0.3147P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0781
_refine_ls_wR_factor_ref         0.0804
_reflns_Friedel_coverage         0.684
_reflns_Friedel_fraction_full    0.977
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                2396
_reflns_number_total             2529
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01951_si_002.cif
_cod_data_source_block           cu_ca031214_1_1_0m
_cod_database_code               4129405
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.710
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S2-C10 \\sim S2-C10A
 with sigma of 0.02
 S1-C9 \\sim S1-C9A
 with sigma of 0.02
 C9-C10A \\sim C9A-C10
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10A)=Sof(H10C)=Sof(H10D)=1-FVAR(1)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C10A(H10C,H10D), C9A(H9AA,H9AB)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C11(H11), C13(H13), C15(H15), C16(H16)
6.d X=CH2 refined with riding coordinates:
 C12(H12A,H12B)
;
_shelx_res_checksum              457
_shelx_hkl_checksum              99595
_olex2_date_sample_data_collection 3.12.2014
_olex2_date_sample_submission    3.12.2014
_olex2_submission_original_sample_id ca031214
_olex2_submission_special_instructions 'No special instructions were received'