Enantio-, Diastereo-, and Regioselective Iridium-Catalyzed Asymmetric Allylic Alkylation of Acyclic β-Ketoesters
Wen-Bo Liu; Corey M. Reeves; Brian M. Stoltz; Journal of the American Chemical Society 135 (2013) 17298–17301; doi:10.1021/ja4097829

data_4121187
_publ_contact_author_address
;
Beckman Institute
Caltech 139-74
Pasadena CA 91125
USA
;
_publ_contact_author_email       xray@caltech.edu
_publ_contact_author_name        'Xray Staff'
_publ_section_title
;
 Enantio-, Diastereo-, and Regioselective Iridium-Catalyzed Asymmetric
 Allylic Alkylation of Acyclic \b-Ketoesters
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17298
_journal_page_last               17301
_journal_paper_doi               10.1021/ja4097829
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H21 Br O2'
_chemical_formula_sum            'C19 H21 Br O2'
_chemical_formula_weight         361.27
_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             2013-09-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466),
 SHELXL-2013,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.871(3)
_cell_length_b                   13.179(3)
_cell_length_c                   21.761(5)
_cell_measurement_reflns_used    9925
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.19
_cell_measurement_theta_min      2.31
_cell_volume                     3404.5(14)
_computing_cell_refinement       'SAINT V8.32B (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2013.6-2 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.32B (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
 and SHELXTL (Bruker-AXS, 2007)
;
_computing_structure_refinement  'SHELXL-2013/2 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXT (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1174
_diffrn_reflns_av_unetI/netI     0.0905
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            88198
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         32.288
_diffrn_reflns_theta_min         1.806
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.420
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6406
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1085 before and 0.0883 after correction.
The Ratio of minimum to maximum transmission is 0.6406.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.410
_exptl_crystal_description       plate
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.704
_refine_diff_density_min         -0.980
_refine_diff_density_rms         0.124
_refine_ls_abs_structure_details
;
 Flack x determined using 3026 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.032(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.307
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     403
_refine_ls_number_reflns         11569
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.307
_refine_ls_R_factor_all          0.0967
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0300P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1052
_refine_ls_wR_factor_ref         0.1137
_reflns_Friedel_coverage         0.788
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                8213
_reflns_number_total             11569
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4097829_si_001.cif
_cod_data_source_block           a13083
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_source_target' value 'MO' changed to 'Mo' according to the
built-in table from CIF Core dictionary named 'cif_core.dic' version
2.4.1 from 2010-06-29.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_cell_volume        3404.5(13)
_cod_database_code               4121187
_cod_database_fobs_code          4121187
_refine_ls_abs_structure_hooft   0.038(5)
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2B(H2BA), C11(H11), C2(H2A), C11B(H11B)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C18B(H18C,H18D)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C8B(H8B), C15(H15), C14(H14), C17(H17), C7B(H7B), C8(H8), C13(H13),
 C16(H16), C4(H4), C5(H5), C9B(H9B), C7(H7), C13B(H13B), C14B(H14B), C4B(H4B),
 C15B(H15B), C17B(H17B), C5B(H5B), C16B(H16B)
2.d X=CH2 refined with riding coordinates:
 C10B(H10C,H10D), C10(H10A,H10B)
2.e Idealised Me refined as rotating group:
 C19B(H19D,H19E,H19F), C19(H19A,H19B,H19C)
2.f Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1B(H1B), O2B(H2B), O2(H2)
;
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.409
_shelxl_version_number           2013-3