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_4127676
_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
;
(1R,3aR,9bS)-1-methyl-3a,4,5,9b-tetrahydronaphtho[2,1-b]furan-2(1H)-one
;
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-15
_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                 106.276(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.79570(10)
_cell_length_b                   13.9632(2)
_cell_length_c                   9.8653(2)
_cell_measurement_reflns_used    8396
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      75.6900
_cell_measurement_theta_min      4.6590
_cell_volume                     1030.83(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      99.98(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 0.982
_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   -114.00  -6.00   0.50    0.07    --  -39.45 -74.00 -63.00  216
  2  \w    -73.00  36.00   0.50    0.07    --  -39.45  74.00  65.00  218
  3  \w    -35.00  73.00   0.50    0.07    --   39.45 -74.00 -63.00  216
  4  \w   -170.00 -61.00   0.50    0.27    --  -94.50 -74.00 -63.00  218
  5  \w    -96.00 -19.00   0.50    0.27    --  -94.50  74.00  65.00  154
  6  \w     39.00  96.00   0.50    0.27    --  114.32 -74.00 -63.00  114
  7  \w     81.00 178.00   0.50    0.27    --  114.32  74.00  65.00  194
  8  \w    -66.00  36.00   0.50    0.07    --  -39.45  57.00-180.00  204
  9  \w    -26.00  43.00   0.50    0.07    --  -39.45  19.00 -60.00  138
 10  \w      6.00 115.00   0.50    0.07    --   39.45  74.00  65.00  218
 11  \w     12.00 115.00   0.50    0.07    --   39.45  57.00-180.00  206
 12  \w    -51.00 -15.00   0.50    0.27    --  -94.50  45.00 -90.00   72
 13  \w    -51.00 -15.00   0.50    0.27    --  -94.50  45.00  30.00   72
 14  \w    -71.00 -19.00   0.50    0.27    --  -94.50  61.00  60.00  104
 15  \w    -71.00 -19.00   0.50    0.27    --  -94.50  61.00 -90.00  104
 16  \w     77.00 178.00   0.50    0.27    --  114.32  30.00-180.00  202
 17  \w     77.00 178.00   0.50    0.27    --  114.32  30.00  30.00  202
 18  \w     85.00 178.00   0.50    0.27    --  114.32  61.00 120.00  186
 19  \w     34.00 109.00   0.50    0.27    --  114.32 -94.00-150.00  150
 20  \w     39.00 106.00   0.50    0.27    --  114.32 -77.00   0.00  134
 21  \w     34.00 109.00   0.50    0.27    --  114.32 -94.00 150.00  150
 22  \w     77.00 178.00   0.50    0.27    --  114.32  30.00-150.00  202
 23  \w     85.00 178.00   0.50    0.27    --  114.32  45.00  90.00  186
 24  \w     34.00 109.00   0.50    0.27    --  114.32 -94.00 -60.00  150
 25  \w     39.00  71.00   0.50    0.27    --  114.32 -61.00 120.00   64
 26  \w   -114.00  -5.00   0.50    0.07    --  -39.45 -77.00  60.00  218
 27  \w   -115.00 -12.00   0.50    0.07    --  -39.45 -57.00-180.00  206
 28  \w    -26.00  43.00   0.50    0.07    --  -39.45  19.00-180.00  138
 29  \w    -26.00  43.00   0.50    0.07    --  -39.45  19.00  90.00  138
 30  \w   -121.00  -7.00   0.50    0.07    --  -39.45 -37.00 -30.00  228
 31  \w      5.00 115.00   0.50    0.07    --   39.45  77.00-120.00  220
 32  \w     58.00 122.00   0.50    0.07    --   39.45-178.00  30.00  128
 33  \w   -170.00 -78.00   0.50    0.27    --  -94.50 -77.00  90.00  184
 34  \w   -170.00 -60.00   0.50    0.27    --  -94.50 -77.00 120.00  220
 35  \w   -170.00 -60.00   0.50    0.27    --  -94.50 -77.00-120.00  220
 36  \w   -170.00 -60.00   0.50    0.27    --  -94.50 -77.00  60.00  220
 37  \w   -170.00 -60.00   0.50    0.27    --  -94.50 -77.00 -30.00  220
 38  \w   -170.00 -60.00   0.50    0.27    --  -94.50 -77.00   0.00  220
 39  \w   -170.00 -60.00   0.50    0.27    --  -94.50 -77.00-180.00  220
 40  \w     85.00 178.00   0.50    0.27    --  114.32  61.00 -60.00  186
 41  \w     39.00  71.00   0.50    0.27    --  114.32 -61.00  60.00   64
 42  \w     77.00 178.00   0.50    0.27    --  114.32  30.00 -90.00  202
;
_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      0.1091565000
_diffrn_orient_matrix_UB_12      0.0903236000
_diffrn_orient_matrix_UB_13      0.0586481000
_diffrn_orient_matrix_UB_21      -0.0815865000
_diffrn_orient_matrix_UB_22      0.0010575000
_diffrn_orient_matrix_UB_23      0.1253392000
_diffrn_orient_matrix_UB_31      0.1542321000
_diffrn_orient_matrix_UB_32      -0.0633517000
_diffrn_orient_matrix_UB_33      0.0855765000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19007
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.477
_diffrn_reflns_theta_min         4.669
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.693
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.620
_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    1.303
_exptl_crystal_description       plate
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.271
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 1829 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         4148
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0431
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0960P)^2^+0.0450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1140
_refine_ls_wR_factor_ref         0.1159
_reflns_Friedel_coverage         0.871
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.931
_reflns_number_gt                4012
_reflns_number_total             4148
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07297_si_005.cif
_cod_data_source_block           exp_47
_cod_database_code               4127676
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
01ed39af90142266e1f7f2ba5a4607aa3f073063466
;
_diffrn_oxdiff_digest_hkl
;
0118fb76bb04b74b3a8841d7ea01b94d595445
;
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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:
 C008(H008), C00F(H00F), C00H(H00H), C00I(H00I), C00O(H00O), C00Q(H00Q)
2.b Secondary CH2 refined with riding coordinates:
 C00J(H00B,H00C), C00M(H00D,H00G), C00R(H00R,H00S), C00U(H00X,H00Y)
2.c Aromatic/amide H refined with riding coordinates:
 C005(H005), C009(H009), C00A(H00A), C00E(H00E), C00K(H00K), C00L(H00L),
 C00N(H00N), C00S(H00T)
2.d Idealised Me refined as rotating group:
 C00P(H00J,H00M,H00P), C00T(H00U,H00V,H00W)
;
_shelx_res_checksum              87792
_shelx_hkl_checksum              72004
_ins_header
;
TITL exp_47 in P2(1)/m 
REM P2(1)/m (#11 in standard setting)
CELL 1.54184   7.795711  13.963248   9.865303  90.0000 106.2761  90.0000
ZERR    4.00   0.000132   0.000194   0.000160   0.0000   0.0018   0.0000
LATT  1
SYMM -x, y+1/2,-z 
SFAC C H N O
UNIT 44.00 40.00 4.00 4.00
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 1.596
_oxdiff_exptl_absorpt_empirical_full_min 0.572