Enantio- and diastereoselective synthesis of substituted tetrahydro-1H-isochromanes through a dynamic kinetic resolution proceeding under dienamine catalysis.
Orue, Ane; Reyes, Efraím; Vicario, Jose L.; Carrillo, Luisa; Uria, Uxue; Organic letters 14 (2012) 3740–3743; doi:10.1021/ol301602h

data_1508307
_publ_section_title
;
 Enantio- and diastereoselective synthesis of substituted
 tetrahydro-1H-isochromanes through a dynamic kinetic resolution
 proceeding under dienamine catalysis.
;
_journal_issue                   14
_journal_name_full               'Organic letters'
_journal_page_first              3740
_journal_page_last               3743
_journal_paper_doi               10.1021/ol301602h
_journal_volume                  14
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C21 H18 O4 S2'
_chemical_formula_sum            'C21 H18 O4 S2'
_chemical_formula_weight         398.47
_space_group_IT_number           5
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      5
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-06-08T13:02:50-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 113.551(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   38.5256(8)
_cell_length_b                   5.85580(10)
_cell_length_c                   17.9538(4)
_cell_measurement_reflns_used    13512
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.4406
_cell_measurement_theta_min      2.5008
_cell_measurement_wavelength     1.54184
_cell_volume                     3712.97(15)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -12.00  130.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756    0.0000  -90.0000 142

  2 omega   25.00   79.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -125.0000   60.0000 54

  3 omega    0.00   53.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756  -38.0000 -120.0000 53

  4 omega   32.00   96.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -125.0000 -120.0000 64

  5 omega    7.00   61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5756 -125.0000  150.0000 54

  6 omega   39.00   77.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000    0.0000 38

  7 omega   87.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000 -180.0000 71

  8 omega   84.00  119.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -119.0000   31.0000 35

  9 omega   96.00  131.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000  -30.0000 35

 10 omega   36.00  143.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000   90.0000 107

 11 omega   45.00   76.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -30.0000 31

 12 omega   79.00  145.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000 -120.0000 66

 13 omega   85.00  121.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  150.0000 36

 14 omega  125.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  150.0000 33

 15 omega   84.00  109.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -104.0000  104.0000 25

 16 omega   79.00  144.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000   30.0000 65

 17 omega  102.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000 -150.0000 56

 18 omega   81.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000   90.0000 77

 19 omega   34.00  127.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000  -90.0000 93

 20 omega   88.00  113.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -104.0000  153.0000 25

 21 omega   37.00   68.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -119.0000   31.0000 31

 22 omega   46.00   77.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -180.0000 31

 23 omega   64.00  113.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -105.0000 -106.0000 49

 24 omega   11.00   45.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   82.0000   74.0000 34

 25 omega   16.00   41.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000  161.0000 25

 26 omega   16.00   45.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   82.0000   22.0000 29

 27 omega   19.00   45.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   82.0000  -75.0000 26

 28 omega   20.00   46.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   80.0000 -144.0000 26

 29 omega   19.00   45.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   82.0000 -178.0000 26

 30 omega   29.00  140.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   75.0000  -40.0000 111

 31 omega -148.00  -43.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -74.0000  -62.0000   92.0000 105

 32 omega -156.00 -129.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 27

 33 omega  -95.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -150.0000 46

 34 omega  -94.00  -49.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 45

 35 omega -137.00  -51.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -68.0000   59.0000 86

 36 omega   79.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000    0.0000 79

 37 omega   79.00  154.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -120.0000 75

 38 omega   79.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -60.0000 79

 39 omega   79.00  157.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000   90.0000 78

 40 omega   79.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -30.0000 79

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0381946
_diffrn_orient_matrix_UB_12      0.0483168
_diffrn_orient_matrix_UB_13      -0.0710694
_diffrn_orient_matrix_UB_21      -0.0174253
_diffrn_orient_matrix_UB_22      0.0640669
_diffrn_orient_matrix_UB_23      0.060903
_diffrn_orient_matrix_UB_31      0.0118389
_diffrn_orient_matrix_UB_32      0.2505279
_diffrn_orient_matrix_UB_33      -0.0017678
_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  0.0302
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24917
_diffrn_reflns_theta_full        75
_diffrn_reflns_theta_max         75
_diffrn_reflns_theta_min         2.5
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    2.813
_exptl_absorpt_correction_T_max  0.916
_exptl_absorpt_correction_T_min  0.648
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
        (compiled Jan 23 2012,18:06:46)
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    1.426
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.3216
_exptl_crystal_size_mid          0.0583
_exptl_crystal_size_min          0.0369
_refine_diff_density_max         0.642
_refine_diff_density_min         -0.532
_refine_diff_density_rms         0.05
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (89%).
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 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.004(6), 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   0.011(14)
_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     529
_refine_ls_number_reflns         7285
_refine_ls_number_restraints     35
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.0393
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0488P)^2^+4.7683P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.1003
_reflns_number_gt                6974
_reflns_number_total             7285
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol301602h_si_001.cif
_cod_data_source_block           ao185
_cod_depositor_comments          'Adding full bibliography for 1508307.cif.'
_cod_original_cell_volume        3712.97(13)
_cod_database_code               1508307