Diastereo- and enantioselective addition of anilide-functionalized allenoates to N-acylimines catalyzed by a pyridylalanine-based peptide.
Mbofana, Curren T.; Miller, Scott J.; Journal of the American Chemical Society 136 (2014) 3285–3292; doi:10.1021/ja412996f

data_4129245
_publ_section_title
;
 Diastereo- and enantioselective addition of anilide-functionalized
 allenoates to N-acylimines catalyzed by a pyridylalanine-based peptide.
;
_journal_issue                   8
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3285
_journal_page_last               3292
_journal_paper_doi               10.1021/ja412996f
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C27 H31 Br N2 O5'
_chemical_formula_sum            'C27 H31 Br N2 O5'
_chemical_formula_weight         543.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-06-18
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                91.596(7)
_cell_angle_beta                 111.824(8)
_cell_angle_gamma                96.479(7)
_cell_formula_units_Z            2
_cell_length_a                   10.3367(3)
_cell_length_b                   11.7642(3)
_cell_length_c                   12.4129(9)
_cell_measurement_reflns_used    15737
_cell_measurement_temperature    293
_cell_measurement_theta_max      63.8
_cell_measurement_theta_min      3.8
_cell_volume                     1388.32(14)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r12 (Rigaku, 2011)'
_computing_molecular_graphics
;
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.
;
_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.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 22.2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
scan:
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	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 0.0000
	             Phi: 0.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 0.0000
	             Phi: 0.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 0.0000
	             Phi: 180.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 0.0000
	             Phi: 180.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 220.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 50.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 125.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 55.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 225.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 300.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 250.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 320.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 110.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 150.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 75.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 350.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 0.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 275.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 25.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 175.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 0.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 325.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: -48.0000 - 132.0000
	     Image width: 2.0000
	        Exp time: 2.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 165.0000
	             XTD: 42.2762
	          2theta: 41.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
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	             Phi: 275.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 100.0000
	             XTD: 42.2762
	          2theta: 89.1828
scan:
	Number of images: 90
	           Slice: 0.0000 - 180.0000
	     Image width: 2.0000
	        Exp time: 15.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	           Kappa: 54.0000
	             Phi: 200.0000
	             XTD: 42.2762
	          2theta: 89.1828
;
_diffrn_measurement_device
;
AFC11 (Left): Eulerian 3 circle
;
_diffrn_measurement_device_type  'Rigaku Saturn 944+ CCD'
_diffrn_measurement_method       \w
_diffrn_measurement_specimen_support Unknown
_diffrn_orient_matrix_type       FS_PROCESS
_diffrn_orient_matrix_UB_11      0.095766
_diffrn_orient_matrix_UB_12      0.013622
_diffrn_orient_matrix_UB_13      0.063118
_diffrn_orient_matrix_UB_21      0.009369
_diffrn_orient_matrix_UB_22      -0.083208
_diffrn_orient_matrix_UB_23      -0.007790
_diffrn_orient_matrix_UB_31      0.042377
_diffrn_orient_matrix_UB_32      0.015871
_diffrn_orient_matrix_UB_33      -0.059412
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1514
_diffrn_reflns_av_unetI/netI     0.0956
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            47221
_diffrn_reflns_theta_full        63.68
_diffrn_reflns_theta_max         63.68
_diffrn_reflns_theta_min         3.79
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_voltage           40.0
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.321
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.763
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R (1998) Private Communication'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         4510
_refine_ls_number_restraints     164
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0602
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1002P)^2^+0.0823P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1685
_refine_ls_wR_factor_ref         0.1782
_reflns_number_gt                3514
_reflns_number_total             4510
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja412996f_si_002.cif
_cod_data_source_block           00713055
_cod_original_cell_volume        1388.32(11)
_cod_database_code               4129245
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2A = N1-H1
 0.91 with sigma of 0.02
3. Rigid bond restraints
 C12, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C24, C25, C27, C26, C27A, C24A, C26A, C25A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C12, C11, C11A, C10A, C12A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C12 \\sim C11: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C26 \\sim C24 \\sim C25 \\sim C27 \\sim C27A \\sim C26A \\sim C24A \\sim C25A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C10 \\sim C12 \\sim C11 \\sim C11A \\sim C10A \\sim C12A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Others
 Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C24A)=Sof(C27A)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C10A)=Sof(H10A)=Sof(C12A)=
 Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(2)
 Sof(C10)=Sof(H10)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C10A(H10A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C2(H2), N1(H1), N2(H2A), C18(H18), C19(H19), C20(H20),
  C21(H21), C22(H22)
6.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C26(H26A,H26B,
 H26C), C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C26A(H26D,H26E,H26F),
 C27A(H27D,H27E,H27F), C25A(H25D,H25E,H25F), C11A(H11D,H11E,H11F), C12A(H12D,
 H12E,H12F)
;