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_4127677
_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         'C18 H15 Cl O2'
_chemical_formula_sum            'C18 H15 Cl O2'
_chemical_formula_weight         298.75
_chemical_name_systematic
;
(3R,3aS,9bR)-8-chloro-3-phenyl-3a,4,5,9b-tetrahydronaphtho[1,2-b]furan-2(3H)-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             2019-02-28
_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                 91.2367(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.74007(4)
_cell_length_b                   24.03214(17)
_cell_length_c                   8.74986(6)
_cell_measurement_reflns_used    19027
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.9790
_cell_measurement_theta_min      3.6660
_cell_volume                     1416.957(16)
_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 0.995
_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    -84.00  31.00   0.50    0.05    --  -39.70  97.00  58.00  230
  2  \w     -9.00  84.00   0.50    0.05    --   39.70 -97.00 -49.00  186
  3  \w    -83.00 -14.00   0.50    0.21    --  -94.50  97.00  58.00  138
  4  \w     36.00 109.00   0.50    0.21    --  116.00 -97.00 -49.00  146
  5  \w    104.00 178.00   0.50    0.21    --  116.00  97.00  58.00  148
  6  \w    -26.00  43.00   0.50    0.05    --  -39.70  19.00   0.00  138
  7  \w    -26.00  43.00   0.50    0.05    --  -39.70  19.00  60.00  138
  8  \w    -26.00  43.00   0.50    0.05    --  -39.70  19.00 -30.00  138
  9  \w     58.00 121.00   0.50    0.05    --   39.70-178.00 -30.00  126
 10  \w     -4.00  85.00   0.50    0.05    --   39.70 -99.00 150.00  178
 11  \w    -45.00  26.00   0.50    0.05    --   39.70 -19.00  90.00  142
 12  \w     -3.00  34.00   0.50    0.05    --   39.70  95.00 120.99   74
 13  \w    -85.00 -14.00   0.50    0.21    --  -94.50 111.00  60.00  142
 14  \w   -175.00 -82.00   0.50    0.21    --  -94.50 -97.00 -49.00  186
 15  \w   -175.00 -80.00   0.50    0.21    --  -94.50 -94.00-120.00  190
 16  \w   -170.00 -68.00   0.50    0.21    --  -94.50 -56.00-135.25  204
 17  \w    -71.00 -19.00   0.50    0.21    --  -94.50  61.00-120.00  104
 18  \w    -51.00 -15.00   0.50    0.21    --  -94.50  45.00   0.00   72
 19  \w     81.00 178.00   0.50    0.21    --  116.00  77.00 120.00  194
 20  \w     60.00 150.00   0.50    0.21    --  116.00 178.00-120.00  180
 21  \w     42.00  71.00   0.50    0.21    --  116.00 -61.00-150.00   58
 22  \w     36.00 111.00   0.50    0.21    --  116.00-111.00  60.00  150
 23  \w     36.00 109.00   0.50    0.21    --  116.00 -94.00 120.00  146
 24  \w     87.00 178.00   0.50    0.21    --  116.00  61.00-180.00  182
 25  \w     87.00 178.00   0.50    0.21    --  116.00  45.00 150.00  182
 26  \w     42.00  71.00   0.50    0.21    --  116.00 -61.00 -60.00   58
 27  \w     81.00 178.00   0.50    0.21    --  116.00  77.00 -90.00  194
 28  \w     42.00  71.00   0.50    0.21    --  116.00 -61.00 -30.00   58
 29  \w     36.00 111.00   0.50    0.21    --  116.00-111.00 -90.00  150
 30  \w     36.00 109.00   0.50    0.21    --  116.00 -94.00-150.00  146
 31  \w     36.00 109.00   0.50    0.21    --  116.00 -94.00-180.00  146
 32  \w     42.00 106.00   0.50    0.21    --  116.00 -77.00 -60.00  128
 33  \w    100.00 178.00   0.50    0.21    --  116.00 111.00  30.00  156
 34  \w     36.00 111.00   0.50    0.21    --  116.00-111.00   0.00  150
 35  \w     36.00 109.00   0.50    0.21    --  116.00 -94.00  90.00  146
 36  \w     42.00 106.00   0.50    0.21    --  116.00 -77.00   0.00  128
 37  \w     36.00 178.00   0.50    0.21    --  116.00  15.00 -30.00  284
 38  \w    100.00 178.00   0.50    0.21    --  116.00 111.00-120.00  156
 39  \w     87.00 178.00   0.50    0.21    --  116.00  45.00 120.00  182
 40  \w     36.00 111.00   0.50    0.21    --  116.00-111.00  90.00  150
 41  \w     36.00 109.00   0.50    0.21    --  116.00 -94.00  30.00  146
 42  \w     36.00 111.00   0.50    0.21    --  116.00-111.00-150.00  150
 43  \w     41.00 126.00   0.50    0.21    --  116.00-136.00  85.15  170
 44  \w     42.00  71.00   0.50    0.21    --  116.00 -61.00  90.00   58
 45  \w    -26.00  43.00   0.50    0.05    --  -39.70  19.00 -90.00  138
 46  \w   -114.00  -5.00   0.50    0.05    --  -39.70 -77.00  60.00  218
 47  \w   -115.00 -12.00   0.50    0.05    --  -39.70 -57.00   0.00  206
 48  \w   -115.00 -12.00   0.50    0.05    --  -39.70 -57.00-120.00  206
 49  \w     -3.00  34.00   0.50    0.05    --   39.70  95.00 156.94   74
 50  \w     13.00 115.00   0.50    0.05    --   39.70  57.00-120.00  204
 51  \w      5.00 114.00   0.50    0.05    --   39.70  77.00 -30.00  218
 52  \w     -3.00  37.00   0.50    0.05    --   39.70  94.00-156.96   80
 53  \w     -2.00  44.00   0.50    0.05    --   39.70  92.00  15.24   92
;
_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      -0.0710919000
_diffrn_orient_matrix_UB_12      0.0601721000
_diffrn_orient_matrix_UB_13      0.0256462000
_diffrn_orient_matrix_UB_21      -0.0546614000
_diffrn_orient_matrix_UB_22      0.0049900000
_diffrn_orient_matrix_UB_23      -0.1713519000
_diffrn_orient_matrix_UB_31      -0.2101687000
_diffrn_orient_matrix_UB_32      -0.0215967000
_diffrn_orient_matrix_UB_33      0.0317410000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            29371
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.361
_diffrn_reflns_theta_min         3.678
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.393
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.606
_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    1.400
_exptl_crystal_description       prism
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.229
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 2798 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     379
_refine_ls_number_reflns         5950
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0264
_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^)+(0.0407P)^2^+0.3745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0694
_refine_ls_wR_factor_ref         0.0702
_reflns_Friedel_coverage         0.937
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                5888
_reflns_number_total             5950
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07297_si_009.cif
_cod_data_source_block           exp_58
_cod_depositor_comments
;

2020-08-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        1416.956(16)
_cod_original_formula_moiety     '2(C18 H15 Cl O2)'
_cod_original_formula_sum        'C36 H30 Cl2 O4'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     597.50
_cod_database_code               4127677
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
01a28e6673982bde9f352b64d6e5d9888f07964d8de
;
_diffrn_oxdiff_digest_hkl
;
01351eda06d2e187b82147f308aad5476989a8
;
_reflns_odcompleteness_completeness 99.97
_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
2.a Ternary CH refined with riding coordinates:
 C12(H12), C32(H32), C3(H3), C22(H22), C31(H31), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C5(H5A,H5B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C37(H37), C17(H17), C10(H10), C36(H36), C8(H8), C7(H7), C40(H40),
 C26(H26), C15(H15), C18(H18), C39(H39), C19(H19), C27(H27), C16(H16), C38(H38)
;
_shelx_res_checksum              7141
_shelx_hkl_checksum              74567
_ins_header
;
TITL exp_58 in P2(1) 
REM P2(1) (#4 in standard setting)
CELL 1.54184   6.740069  24.032137   8.749856  90.0000  91.2367  90.0000
ZERR    6.00   0.000036   0.000169   0.000057   0.0000   0.0006   0.0000
LATT -1
SYMM -x, y+1/2,-z 
SFAC C H N O
UNIT 66.00 60.00 6.00 6.00
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 1.349
_oxdiff_exptl_absorpt_empirical_full_min 0.765