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_4127679
_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         'C12 H11 Cl O2'
_chemical_formula_sum            'C12 H11 Cl O2'
_chemical_formula_weight         222.66
_chemical_name_systematic
;
(3aS,9bR)-8-chloro-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             2019-02-15
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.98860(10)
_cell_length_b                   7.73610(10)
_cell_length_c                   26.4469(4)
_cell_measurement_reflns_used    6203
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.4600
_cell_measurement_theta_min      3.3390
_cell_volume                     1020.65(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      99.99(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 0.988
_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   -103.00 -18.00   0.50    0.05    --  -39.70 141.00  94.00  170
  2  \w    -83.00 -13.00   0.50    0.05    --  -94.50  95.00  31.00  140
  3  \w   -177.00 -55.00   0.50    0.05    --  -94.50 -28.00  68.00  244
  4  \w     37.00 119.00   0.50    0.05    --  114.32-128.00-151.00  164
  5  \w    -26.00  43.00   0.50    0.05    --  -39.70  19.00 -60.00  138
  6  \w     -4.00  85.00   0.50    0.05    --   39.70 -99.00  90.00  178
  7  \w    -51.00 -15.00   0.50    0.05    --  -94.50  45.00-120.00   72
  8  \w     39.00  71.00   0.50    0.05    --  114.32 -61.00  90.00   64
  9  \w     39.00  71.00   0.50    0.05    --  114.32 -61.00 -30.00   64
 10  \w     39.00  71.00   0.50    0.05    --  114.32 -61.00-180.00   64
 11  \w     39.00  71.00   0.50    0.05    --  114.32 -61.00-150.00   64
 12  \w     92.00 178.00   0.50    0.05    --  114.32 125.00-150.00  172
 13  \w     33.00 108.00   0.50    0.05    --  114.32 -95.00 -78.00  150
 14  \w     39.00  71.00   0.50    0.05    --  114.32 -61.00 -60.00   64
 15  \w     39.00  71.00   0.50    0.05    --  114.32 -61.00 120.00   64
 16  \w     77.00 178.00   0.50    0.05    --  114.32  30.00-120.00  202
 17  \w   -115.00 -12.00   0.50    0.05    --  -39.70 -57.00  60.00  206
 18  \w   -117.00 -69.00   0.50    0.05    --  -39.70-128.00-151.00   96
 19  \w   -114.00  -5.00   0.50    0.05    --  -39.70 -77.00 -30.00  218
 20  \w   -115.00 -12.00   0.50    0.05    --  -39.70 -57.00-180.00  206
 21  \w   -170.00 -60.00   0.50    0.05    --  -94.50 -77.00-180.00  220
 22  \w   -170.00 -65.00   0.50    0.05    --  -94.50 -61.00-120.00  210
 23  \w   -174.00 -65.00   0.50    0.05    --  -94.50 -45.00 -30.00  218
 24  \w     35.00  97.00   0.50    0.05    --  114.32  15.00  90.00  124
;
_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      -0.2642152000
_diffrn_orient_matrix_UB_12      -0.0819036000
_diffrn_orient_matrix_UB_13      0.0183073000
_diffrn_orient_matrix_UB_21      0.1140610000
_diffrn_orient_matrix_UB_22      -0.1812947000
_diffrn_orient_matrix_UB_23      -0.0108929000
_diffrn_orient_matrix_UB_31      0.1119963000
_diffrn_orient_matrix_UB_32      -0.0088014000
_diffrn_orient_matrix_UB_33      0.0542208000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            9699
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.400
_diffrn_reflns_theta_min         3.342
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.109
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.405
_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    1.449
_exptl_crystal_description       prism
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.379
_exptl_crystal_size_mid          0.223
_exptl_crystal_size_min          0.144
_refine_diff_density_max         0.193
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 771 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.940
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     136
_refine_ls_number_reflns         2088
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.940
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0322
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1020
_refine_ls_wR_factor_ref         0.1057
_reflns_Friedel_coverage         0.638
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                2037
_reflns_number_total             2088
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07297_si_003.cif
_cod_data_source_block           exp_46
_cod_database_code               4127679
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
01d9c0e9d64be7c6237256d31bb8cfa0b103512b9b6
;
_diffrn_oxdiff_digest_hkl
;
01004c4b10b8ac4a5f79bc276960f23e8956a0
;
_reflns_odcompleteness_completeness 99.91
_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
2.a Ternary CH refined with riding coordinates:
 C00B(H00C), C00D(H00F)
2.b Secondary CH2 refined with riding coordinates:
 C007(H00A,H00B), C00C(H00D,H00E), C00F(H00G,H00H)
2.c Aromatic/amide H refined with riding coordinates:
 C005(H005), C006(H006), C009(H009)
;
_shelx_res_checksum              67461
_shelx_hkl_checksum              63522
_ins_header
;
TITL exp_46 in P2(1)2(1)2(1) 
REM P2(1)2(1)2(1) (#19 in standard setting)
CELL 1.54184   4.988550   7.736078  26.446929  90.0000  90.0000  90.0000
ZERR    4.00   0.000073   0.000101   0.000444   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 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 2.059
_oxdiff_exptl_absorpt_empirical_full_min 0.495