Exploring the vinylogous reactivity of cyclohexenylidene malononitriles: switchable regioselectivity in the organocatalytic asymmetric addition to enals giving highly enantioenriched carbabicyclic structures.
Dell'Amico, Luca; Rassu, Gloria; Zambrano, Vincenzo; Sartori, Andrea; Curti, Claudio; Battistini, Lucia; Pelosi, Giorgio; Casiraghi, Giovanni; Zanardi, Franca; Journal of the American Chemical Society 136 (2014) 11107–11114; doi:10.1021/ja5054576

data_4122317
_publ_section_title
;
 Exploring the vinylogous reactivity of cyclohexenylidene malononitriles:
 switchable regioselectivity in the organocatalytic asymmetric addition to
 enals giving highly enantioenriched carbabicyclic structures.
;
_journal_issue                   31
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11107
_journal_page_last               11114
_journal_paper_doi               10.1021/ja5054576
_journal_volume                  136
_journal_year                    2014
_chemical_formula_sum            'C19 H18 N2 O'
_chemical_formula_weight         290.35
_chemical_name_systematic
;
2-[(1S,4S,5R,6S)-5-Formyl-4-methyl-6-phenylbicyclo[2.2.2]
octan-2-ylidene]malononitrile
;
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 96.979(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.4215(9)
_cell_length_b                   6.9754(8)
_cell_length_c                   13.365(2)
_cell_measurement_temperature    293(2)
_cell_volume                     779.29(17)
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0213
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8439
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.531
_diffrn_reflns_theta_min         1.535
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  0.74
_exptl_absorpt_correction_T_min  0.66
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       prism
_exptl_crystal_F_000             308
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.147
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1531 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         3571
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0328
_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^)+(0.0540P)^2^+0.0771P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0878
_refine_ls_wR_factor_ref         0.0885
_reflns_Friedel_coverage         0.837
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                3469
_reflns_number_total             3571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5054576_si_002.cif
_cod_data_source_block           7a
_cod_depositor_comments
'Adding full bibliography for 4122316--4122317.cif.'
_cod_original_cell_volume        779.31(17)
_cod_database_code               4122317
_shelxl_version_number           2014-3
_shelx_res_checksum              91887
_shelx_hkl_checksum              42217