Diastereoselective Synthesis of α-Quaternary Aziridine-2-carboxylates via Aza-Corey-Chaykovsky Aziridination of N-tert-Butanesulfinyl Ketimino Esters.
Marsini, Maurice A.; Reeves, Jonathan T.; Desrosiers, Jean-Nicolas; Herbage, Melissa A.; Savoie, Jolaine; Li, Zhibin; Fandrick, Keith R.; Sader, C. Avery; McKibben, Bryan; Gao, Donghong A.; Cui, Jianwen; Gonnella, Nina C.; Lee, Heewon; Wei, Xudong; Roschangar, Frank; Lu, Bruce Z.; Senanayake, Chris H.; Organic letters 17 (2015) 5614–5617; doi:10.1021/acs.orglett.5b02838

data_1540608
_publ_section_title
;
 Diastereoselective Synthesis of \a-Quaternary Aziridine-2-carboxylates
 via Aza-Corey-Chaykovsky Aziridination of N-tert-Butanesulfinyl Ketimino
 Esters.
;
_journal_issue                   22
_journal_name_full               'Organic letters'
_journal_page_first              5614
_journal_page_last               5617
_journal_paper_doi               10.1021/acs.orglett.5b02838
_journal_volume                  17
_journal_year                    2015
_chemical_formula_moiety         'C32 H37 Br Cl N3 O6 S2'
_chemical_formula_sum            'C32 H37 Br Cl N3 O6 S2'
_chemical_formula_weight         739.12
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-10-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                75.0450(10)
_cell_angle_beta                 78.8930(10)
_cell_angle_gamma                69.6590(10)
_cell_formula_units_Z            2
_cell_length_a                   9.9554(3)
_cell_length_b                   13.0776(4)
_cell_length_c                   14.9103(4)
_cell_measurement_reflns_used    9419
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.499
_cell_measurement_theta_min      3.087
_cell_volume                     1747.12(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.948
_diffrn_measured_fraction_theta_max 0.948
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0532
_diffrn_reflns_Laue_measured_fraction_full 0.948
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12422
_diffrn_reflns_point_group_measured_fraction_full 0.718
_diffrn_reflns_point_group_measured_fraction_max 0.718
_diffrn_reflns_theta_full        66.494
_diffrn_reflns_theta_max         66.494
_diffrn_reflns_theta_min         3.088
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.803
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5833
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       prism
_exptl_crystal_F_000             764
_refine_diff_density_max         1.286
_refine_diff_density_min         -0.840
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 2850 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.032(7)
_refine_ls_extinction_coef       0.0054(3)
_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   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     839
_refine_ls_number_reflns         8863
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0646P)^2^+0.6682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.514
_reflns_Friedel_fraction_full    0.487
_reflns_Friedel_fraction_max     0.487
_reflns_number_gt                8714
_reflns_number_total             8863
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02838_si_004.cif
_cod_data_source_block           scan_0m_p1_a
_cod_database_code               1540608
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H34A)=Sof(H34B)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=1-FVAR(1)
 Sof(H34C)=Sof(H34D)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C0AA(H0AA), C54(H54), C22(H22), C36(H36), C23(H23), C55(H55)
3.b Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C8(H8A,H8B), C2(H2A,H2B), C34(H34A,H34B), C34(H34C,H34D)
3.c Aromatic/amide H refined with riding coordinates:
 N5(H5), N2(H2), N6(H6), N3(H3), C16(H16), C52(H52), C49(H49), C17(H17),
 C20(H20), C46(H46), C48(H48), C60(H60), C19(H19), C51(H51), C27(H27), C10(H10),
  C63(H63), C59(H59), C28(H28), C42(H42), C62(H62), C13(H13), C14(H14),
 C31(H31), C12(H12), C45(H45), C44(H44), C30(H30)
3.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C5(H5A,H5B,H5C), C37(H37A,H37B,H37C), C56(H56A,H56B,
 H56C), C25(H25A,H25B,H25C), C57(H57A,H57B,H57C), C64(H64A,H64B,H64C), C32(H32A,
 H32B,H32C), C1(H1A,H1B,H1C), C2AA(H2AA,H2AB,H2AC), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              47837
_shelx_hkl_checksum              89535
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'