Beyond Classical Reactivity Patterns: Shifting from 1,4- to 1,6-Additions in Regio- and Enantioselective Organocatalyzed Vinylogous Reactions of Olefinic Lactones with Enals and 2,4-Dienals
Luca Dell'Amico; Łukasz Albrecht; Tricia Naicker; Pernille H. Poulsen; Karl Anker Jørgensen; Journal of the American Chemical Society 135 (2013) 8063–8070; doi:10.1021/ja4029928

data_4119814
_publ_section_title
;
 Beyond Classical Reactivity Patterns: Shifting from 1,4- to 1,6-Additions
 in Regio- and Enantioselective Organocatalyzed Vinylogous Reactions of
 Olefinic Lactones with Enals and 2,4-Dienals
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8063
_journal_page_last               8070
_journal_paper_doi               10.1021/ja4029928
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C27 H25 N O4'
_chemical_formula_sum            'C27 H25 N O4'
_chemical_formula_weight         427.48
_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'
_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_date             2013-03-22
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_audit_update_record
;
2013-03-28 # Formatted by publCIF
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.67519(13)
_cell_length_b                   13.1864(2)
_cell_length_c                   19.5646(2)
_cell_measurement_reflns_used    7206
_cell_measurement_temperature    99.94(18)
_cell_measurement_theta_max      28.3881
_cell_measurement_theta_min      1.5412
_cell_volume                     2238.08(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_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
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      99.94(18)
_diffrn_detector_area_resol_mean 10.3590
_diffrn_measured_fraction_theta_full 0.9996
_diffrn_measured_fraction_theta_max 0.9962
_diffrn_measurement_details
;
  1 omega    8.00   95.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9221   77.0000  120.0000 87

  2 omega  -61.00   17.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0940   57.0000  120.0000 78

  3 omega  -13.00   27.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0940  -99.0000  -90.0000 40

  4 omega  -77.00   66.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9221  -57.0000 -180.0000 143

  5 omega -120.00    8.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.0940  -57.0000 -150.0000 128
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_UB_11      0.0526447000
_diffrn_orient_matrix_UB_12      0.0394229000
_diffrn_orient_matrix_UB_13      0.0079598000
_diffrn_orient_matrix_UB_21      0.0582626000
_diffrn_orient_matrix_UB_22      -0.0365458000
_diffrn_orient_matrix_UB_23      0.0063264000
_diffrn_orient_matrix_UB_31      0.0226312000
_diffrn_orient_matrix_UB_32      0.0023707000
_diffrn_orient_matrix_UB_33      -0.0348055000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            19585
_diffrn_reflns_theta_full        27.50
_diffrn_reflns_theta_max         28.45
_diffrn_reflns_theta_min         1.86
_diffrn_source                   ' 'SuperNova (Mo) x-ray Source'
_exptl_absorpt_coefficient_mu    0.085
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92077
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       irregular
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.163
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -1.2(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     294
_refine_ls_number_reflns         5239
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0337P)^2^+0.2415P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0791
_refine_ls_wR_factor_ref         0.0867
_reflns_number_gt                4376
_reflns_number_total             5239
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja4029928_si_002.cif
_cod_data_source_block           2013_03_21b
_cod_original_cell_volume        2238.09(6)
_cod_database_code               4119814
_cod_database_fobs_code          4119814
_chemical_oxdiff_formula         'C20 H20 O4'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H32A,H32B} of C32, H7 of C7, H16 of C16, H17 of C17, H18 of C18, H20 of
  C20, H21 of C21, H22 of C22, H23 of C23, H24 of C24, H25 of C25, H26 of C26,
  H27 of C27, H28 of C28, H29 of C29, H15 of C15, H14 of C14, {H13A,H13B} of
  C13, H12 of C12
 At 1.5 times of:
  {H31A,H31B,H31C} of C31
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C32(H32A,H32B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C29(H29)
2.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C)
;