l-Isoleucine derived bifunctional phosphine catalyses asymmetric [3 + 2]-annulation of allenyl-esters and -ketones with ketimines
Sankar, Muthukumar G.; Garcia-Castro, Miguel; Golz, Christopher; Strohmann, Carsten; Kumar, Kamal; RSC Adv. 6 (2016) 56537–; doi:10.1039/C6RA12387B

data_7225519
_publ_section_title
;
 l-Isoleucine derived bifunctional phosphine catalyses asymmetric [3 +
 2]-annulation of allenyl-esters and -ketones with ketimines
;
_journal_issue                   61
_journal_name_full               'RSC Adv.'
_journal_page_first              56537
_journal_paper_doi               10.1039/C6RA12387B
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H25 Br N2 O5'
_chemical_formula_sum            'C25 H25 Br N2 O5'
_chemical_formula_weight         513.38
_chemical_name_systematic
'3'-benzyl 1'-(tert-butyl) (R)-5-bromo-1-methyl-2-oxo-1,2,5'-trihydrospiro[indole-3,2'-pyrrole]-1',3'-dicarboxylate'
_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     direct
_audit_creation_date             2016-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-04-04 deposited with the CCDC.
2016-06-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.810(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.001(2)
_cell_length_b                   9.362(2)
_cell_length_c                   14.597(3)
_cell_measurement_reflns_used    468
_cell_measurement_temperature    100
_cell_measurement_theta_max      20.56
_cell_measurement_theta_min      3.20
_cell_volume                     1189.2(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker D8 VENTURE area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS PHOTON100 area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'HELIOS mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            51392
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.993
_diffrn_reflns_theta_min         2.415
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.767
_exptl_absorpt_correction_T_max  0.1259
_exptl_absorpt_correction_T_min  0.0878
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0985 before and 0.0424 after correction. The Ratio of minimum to maximum transmission is 0.6974. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.434
_exptl_crystal_description       plate
_exptl_crystal_F_000             528
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.146
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2794 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0072(15)
_refine_ls_extinction_coef       0.0076(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         6317
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0217
_refine_ls_R_factor_gt           0.0207
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0280P)^2^+0.2997P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0525
_refine_ls_wR_factor_ref         0.0530
_reflns_Friedel_coverage         0.889
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6144
_reflns_number_total             6317
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra12387b2.cif
_cod_data_source_block           mo_b0269_0m
_cod_original_cell_volume        1189.2(5)
_cod_database_code               7225519
_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 Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C16(H16), C17(H17), C5(H5), C11(H11), C18(H18), C20(H20), C7(H7),
 C19(H19)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C2(H2A,H2B,H2C)
;
_shelx_res_checksum              97069
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_solvent_exptl_crystal_recrystallization_method 'Ethylacetate/ Petrolether'