Multiple Absolute Stereocontrol in Cascade Lactone Formation via Dynamic Kinetic Resolution Driven by the Asymmetric Transfer Hydrogenation of Keto Acids with Oxo-Tethered Ruthenium Catalysts.
Touge, Taichiro; Sakaguchi, Kazuhiko; Tamaki, Nao; Nara, Hideki; Yokozawa, Tohru; Matsumura, Kazuhiko; Kayaki, Yoshihito; Journal of the American Chemical Society 141 (2019) 16354–16361; doi:10.1021/jacs.9b07297

data_4127673
_publ_section_title
;
 Multiple Absolute Stereocontrol in Cascade Lactone Formation via Dynamic
 Kinetic Resolution Driven by the Asymmetric Transfer Hydrogenation of
 Keto Acids with Oxo-Tethered Ruthenium Catalysts.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16354
_journal_page_last               16361
_journal_paper_doi               10.1021/jacs.9b07297
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H14 O2'
_chemical_formula_sum            'C13 H14 O2'
_chemical_formula_weight         202.24
_chemical_name_systematic
;
(3R,3aS,9bR)-3-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-b]furan-2(3H)-one
;
_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     dual
_audit_creation_date             2019-02-28
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.05 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5625)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.03220(10)
_cell_length_b                   13.0715(2)
_cell_length_c                   16.2633(2)
_cell_measurement_reflns_used    6055
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.2510
_cell_measurement_theta_min      4.3490
_cell_volume                     1069.77(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -26.00  43.00   0.50    0.46    --  -39.45  19.00  90.00  138
  2  \w    -26.00  43.00   0.50    0.46    --  -39.45  19.00 150.00  138
  3  \w     12.00 114.00   0.50    0.46    --   39.45  58.00 159.00  204
  4  \w      5.00 115.00   0.50    0.46    --   39.45  77.00 -30.00  220
  5  \w     87.00 178.00   0.50    1.83    --  116.00  45.00-150.00  182
  6  \w    100.00 178.00   0.50    1.83    --  116.00 111.00  30.00  156
  7  \w     88.00 178.00   0.50    1.83    --  116.00  58.00 159.00  180
  8  \w     87.00 178.00   0.50    1.83    --  116.00  45.00  90.00  182
  9  \w     87.00 178.00   0.50    1.83    --  116.00  61.00  90.00  182
 10  \w     41.00  67.00   0.50    1.83    --  116.00 -58.00  18.00   52
 11  \w     42.00  71.00   0.50    1.83    --  116.00 -61.00  60.00   58
 12  \w     42.00  71.00   0.50    1.83    --  116.00 -61.00 120.00   58
 13  \w     42.00  71.00   0.50    1.83    --  116.00 -61.00 150.00   58
 14  \w     37.00 113.00   0.50    1.83    --  116.00-120.00 144.00  152
 15  \w     46.00 137.00   0.50    1.83    --  116.00-154.00 -13.00  182
 16  \w     42.00  74.00   0.50    1.83    --  116.00 -63.00-145.00   64
 17  \w     42.00  71.00   0.50    1.83    --  116.00 -61.00 -30.00   58
 18  \w     42.00  71.00   0.50    1.83    --  116.00 -61.00   0.00   58
 19  \w     36.00 111.00   0.50    1.83    --  116.00-111.00   0.00  150
 20  \w     46.00 116.00   0.50    0.46    --   39.45-154.00 -13.00  140
 21  \w     36.00 178.00   0.50    1.83    --  116.00  15.00   0.00  284
 22  \w      5.00 115.00   0.50    0.46    --   39.45  77.00-150.00  220
 23  \w    -26.00  43.00   0.50    0.46    --  -39.45  19.00-120.00  138
 24  \w    -45.00  26.00   0.50    0.46    --   39.45 -19.00-120.00  142
 25  \w    -74.00 -19.00   0.50    1.83    --  -94.50  63.00  -8.00  110
 26  \w    -51.00 -15.00   0.50    1.83    --  -94.50  45.00 -90.00   72
 27  \w    -51.00 -15.00   0.50    1.83    --  -94.50  45.00 -30.00   72
 28  \w    -51.00 -15.00   0.50    1.83    --  -94.50  45.00  60.00   72
 29  \w   -114.00  -5.00   0.50    0.46    --  -39.45 -77.00  30.00  218
 30  \w   -170.00 -86.00   0.50    1.83    --  -94.50 -77.00  60.00  168
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0046601000
_diffrn_orient_matrix_UB_12      0.0186322000
_diffrn_orient_matrix_UB_13      -0.0935190000
_diffrn_orient_matrix_UB_21      0.2103616000
_diffrn_orient_matrix_UB_22      -0.0847084000
_diffrn_orient_matrix_UB_23      -0.0099566000
_diffrn_orient_matrix_UB_31      -0.2222855000
_diffrn_orient_matrix_UB_32      -0.0798368000
_diffrn_orient_matrix_UB_33      -0.0112997000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10688
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.500
_diffrn_reflns_theta_min         4.339
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.644
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       prism
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.202
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.198
_refine_diff_density_min         -0.145
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 854 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     137
_refine_ls_number_reflns         2238
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0309
_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^)+(0.0526P)^2^+0.1499P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0852
_refine_ls_wR_factor_ref         0.0861
_reflns_Friedel_coverage         0.663
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                2161
_reflns_number_total             2238
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07297_si_011.cif
_cod_data_source_block           exp_57
_cod_database_code               4127673
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
015e426d93ae2d99f9eea1b1656764090b04108fb30
;
_diffrn_oxdiff_digest_hkl
;
01e3d191eb183623ceae5132827ef50bef0d9f
;
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C13(H13), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C8(H8), C9(H9), C10(H10)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              47367
_shelx_hkl_checksum              37277
_ins_header
;
TITL exp_57 in P2(1)2(1)2(1) 
REM P2(1)2(1)2(1) (#19 in standard setting)
CELL 1.54184   5.032169  13.071543  16.263274  90.0000  90.0000  90.0000
ZERR    5.00   0.000072   0.000212   0.000222   0.0000   0.0000   0.0000
LATT -1
SYMM -x+1/2,-y, z+1/2 
SYMM -x, y+1/2,-z+1/2 
SYMM  x+1/2,-y+1/2,-z 
SFAC C H N O
UNIT 55.00 50.00 5.00 5.00
TREF
HKLF 4
END
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.503
_oxdiff_exptl_absorpt_empirical_full_min 0.704