Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1,4-addition/Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights.
Orue, Ane; Uria, Uxue; Roca-López, David; Delso, Ignacio; Reyes, Efraím; Carrillo, Luisa; Merino, Pedro; Vicario, Jose L.; Chemical science 8 (2017) 2904–2913; doi:10.1039/c7sc00009j

data_1545176
_publ_section_title
;
 Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade
 1,4-addition/Michael reaction through dynamic kinetic resolution under
 iminium catalysis. Development and mechanistic insights.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              2904
_journal_page_last               2913
_journal_paper_doi               10.1039/c7sc00009j
_journal_volume                  8
_journal_year                    2017
_chemical_absolute_configuration 2R,3S,3aR,7aS
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C13 H20 O4'
_chemical_formula_sum            'C13 H20 O4'
_chemical_formula_weight         240.29
_chemical_name_systematic
;
 (2R,3S,3aR,7aS)-5-Oxo-2-pentylhexahydro-4H-furo[2,3-b]pyran-3-carbaldehyde
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_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             2014-06-09T23:07:07-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2017-01-02 deposited with the CCDC.
2017-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.56040(10)
_cell_length_b                   6.68950(10)
_cell_length_c                   33.0826(5)
_cell_measurement_reflns_used    9940
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.683
_cell_measurement_theta_min      5.324
_cell_measurement_wavelength     1.54184
_cell_volume                     1230.55(3)
_computing_cell_refinement       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_collection       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_reduction        'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_molecular_graphics    'Diamond v.3.2f (Crystal Impact GbR, 2008)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'OLEX2 (Dolomanov et al, 2009)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -82.00  -12.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  125.0000  150.0000 70

  2 omega   18.00   78.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506   37.0000 -150.0000 60

  3 omega   83.00  109.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506   37.0000 -150.0000 26

  4 omega  -34.00   -8.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   45.0000   30.0000 26

  5 omega   90.00  116.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000 -150.0000 26

  6 omega   94.00  153.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000   30.0000 59

  7 omega   38.00   69.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000    0.0000 31

  8 omega   35.00   61.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   30.0000 26

  9 omega   43.00   81.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000 -150.0000 38

 10 omega   65.00  111.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -100.0000    7.0000 46

 11 omega   33.00  150.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -15.0000 -180.0000 117

 12 omega   31.00   69.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   60.0000 38

 13 omega  -53.00   23.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506   37.0000  120.0000 76

 14 omega    7.00  107.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506   77.0000  -60.0000 100

 15 omega  -76.00  -50.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   45.0000  120.0000 26

 16 omega   75.00  126.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000   30.0000 51

 17 omega   67.00  104.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -60.0000 37

 18 omega   35.00   61.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000   30.0000 26

 19 omega   70.00  139.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -61.0000  120.0000 69

 20 omega   34.00   60.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -61.0000  120.0000 26

 21 omega   34.00  105.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  -60.0000 71

 22 omega   30.00   55.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -60.0000 25

 23 omega   43.00   68.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  -90.0000 25

 24 omega   60.00  133.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   15.0000 -120.0000 73

 25 omega   43.00   73.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  -60.0000 30

 26 omega -120.00   -7.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -77.0000  120.0000 113

 27 omega -117.00  -15.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9506  -37.0000  -30.0000 102

 28 omega   11.00  115.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506   57.0000 -120.0000 104

 29 omega    2.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506 -125.0000  -30.0000 96

 30 omega   11.00  115.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9506   57.0000   90.0000 104

 31 omega -157.00  -53.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -61.0000 -180.0000 104

 32 omega -162.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   90.0000 113

 33 omega -162.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -30.0000 113

 34 omega -162.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -120.0000 113

 35 omega -162.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  150.0000 113

 36 omega -162.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   30.0000 113

 37 omega -162.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 113

 38 omega   30.00   69.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -30.0000 39

 39 omega   81.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   45.0000  -90.0000 77

 40 omega   78.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000  -30.0000 80

 41 omega   75.00  144.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   77.0000   30.0000 69

 42 omega   78.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000  150.0000 80

 43 omega   75.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   77.0000  -30.0000 83

 44 omega   78.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000   90.0000 80

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0233104
_diffrn_orient_matrix_UB_12      -0.1098188
_diffrn_orient_matrix_UB_13      0.0407522
_diffrn_orient_matrix_UB_21      0.10786
_diffrn_orient_matrix_UB_22      -0.1897494
_diffrn_orient_matrix_UB_23      -0.0191726
_diffrn_orient_matrix_UB_31      0.2541132
_diffrn_orient_matrix_UB_32      0.0704332
_diffrn_orient_matrix_UB_33      0.0118727
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Cu) X-ray micro-source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            22597
_diffrn_reflns_theta_full        71
_diffrn_reflns_theta_max         71
_diffrn_reflns_theta_min         2.67
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.779
_exptl_absorpt_correction_T_max  0.979
_exptl_absorpt_correction_T_min  0.921
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
        (compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.1821
_exptl_crystal_size_mid          0.0405
_exptl_crystal_size_min          0.0323
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.156
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (99%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using PLATON (Spek, 2011).
 The results indicated that the absolute structure had been correctly
 assigned. The method calculated that the probability that the structure 
is inverted is smaller than 10-51. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.12(7), which together with Flack parameter 
value, indicate that the absolute structure has sureley been determined 
correctly.

Flack, H. D. (1983), Acta Cryst. A39, 876-881
Flack & G. Bernardinelli, Acta Cryst. 1999, A55, 908-915; 
H. D. Flack & G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143-1148.

R. W. W. Hooft, L. H. Straver & A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103
A. L. Spek (2010) PLATON, Utrecht, The Netherlands; 
A. L. Spek, J. Appl. Cryst. 2003, 36, 7-13
A. L. Thompson & D. J. Watkin, Tetrahedron: Asymmetry 2009, 20, 712--717

;
_refine_ls_abs_structure_Flack   -0.13(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    noref
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2369
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0306
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0294P)^2^+0.3652P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0711
_reflns_number_gt                2283
_reflns_number_total             2369
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            c7sc00009j2.cif
_cod_data_source_block           a2014049_ao509_rem
_cod_depositor_comments
;Adding full bibliography for 1545175--1545177.cif.

 Adding full bibliography for 1545175--1545177.cif.
;
_cod_database_code               1545176