Highly diastereoselective radical cyclisations of chiral sulfinimines
Elise M. Rochette; William Lewis; Al G. Dossetter; Robert A. Stockman; Chem.Commun. 49 (2013) 9395–; doi:10.1039/c3cc45452e

data_7109851
_publ_section_title
;
 Highly diastereoselective radical cyclisations of chiral sulfinimines
;
_journal_name_full               Chem.Commun.
_journal_page_first              9395
_journal_paper_doi               10.1039/c3cc45452e
_journal_volume                  49
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H29 N O S'
_chemical_formula_sum            'C19 H29 N O S'
_chemical_formula_weight         319.49
_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_Hall           'P 31'
_space_group_name_H-M_alt        'P 31'
_symmetry_space_group_name_Hall  'P 31'
_symmetry_space_group_name_H-M   'P 31'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-05-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   20.64863(14)
_cell_length_b                   20.64863(14)
_cell_length_c                   11.23270(10)
_cell_measurement_reflns_used    37205
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      77.7060
_cell_measurement_theta_min      4.2630
_cell_volume                     4147.60(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
;
_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, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 10.6296
_diffrn_measured_fraction_theta_full 0.9992
_diffrn_measured_fraction_theta_max 0.9615
_diffrn_measurement_details
;
  1 omega  -92.00   -2.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000   30.0000 90

  2 omega  -55.00  -18.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   45.0000 -120.0000 37

  3 omega  -53.00   31.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   45.0000   30.0000 84

  4 omega   10.00   43.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   77.0000 -180.0000 33

  5 omega   42.00   94.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   38.0000 -120.0000 52

  6 omega   48.00   75.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   19.0000 -150.0000 27

  7 omega   14.00   88.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   57.0000  -90.0000 74

  8 omega   79.00  105.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   81.0000  137.0488 26

  9 omega  117.00  163.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000  122.8287 46

 10 omega  138.00  164.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   66.0000  132.9894 26

 11 omega   78.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   85.0000 -150.7737 26

 12 omega   43.00   72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000 -111.0000  -90.0000 29

 13 omega   83.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000 -111.0000  -90.0000 32

 14 omega   33.00   66.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -94.0000   30.0000 33

 15 omega   78.00  119.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   83.0000 -178.6685 41

 16 omega   84.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   66.0000 -153.2656 27

 17 omega   86.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000  122.8287 25

 18 omega   47.00  118.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -61.0000  -60.0000 71

 19 omega   80.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   77.0000 -150.0000 26

 20 omega   88.00  173.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   45.0000  -30.0000 85

 21 omega   84.00  125.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000 -180.0000 41

 22 omega  150.00  176.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000 -180.0000 26

 23 omega   38.00   83.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -29.0000  -79.0000 45

 24 omega   80.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   77.0000 -180.0000 26

 25 omega   80.00  105.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   77.0000  150.0000 25

 26 omega  116.00  141.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   77.0000  150.0000 25

 27 omega   45.00   96.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -45.0000   30.0000 51

 28 omega   84.00  118.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000  150.0000 34

 29 omega   80.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000 -111.0000 -180.0000 26

 30 omega   75.00  101.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -94.0000   30.0000 26

 31 omega  118.00  176.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   85.0000  125.0532 58

 32 omega   75.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000 -111.0000 -150.0000 25

 33 omega   38.00   72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000 -111.0000 -150.0000 34

 34 omega   64.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -30.0000  120.0000 26

 35 omega  132.00  164.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   30.0000 -120.0000 32

 36 omega   89.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   45.0000 -180.0000 88

 37 omega   92.00  118.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   45.0000  150.0000 26

 38 omega  149.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000    0.0000 29

 39 omega   88.00  135.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000    0.0000 47

 40 omega   73.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -45.0000   60.0000 25

 41 omega   78.00  103.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   85.0000  125.0532 25

 42 omega   83.00  173.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   64.0000 -172.3706 90

 43 omega   84.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000 -150.0000 26

 44 omega   86.00  119.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000  -61.0000   60.0000 33

 45 omega   83.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   66.0000  132.9894 26

 46 omega   86.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   56.0000  176.2770 25

 47 omega -109.00  -50.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000 -160.0000   55.0000 59

 48 omega   14.00  108.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   57.0000  -30.0000 94

 49 omega   19.00  110.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   38.0000 -180.0000 91

 50 omega    9.00  111.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   77.0000 -120.0000 102

 51 omega    2.00   93.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804 -125.0000  -30.0000 91

 52 omega   14.00  108.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   57.0000   30.0000 94

 53 omega    9.00  111.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.1804   77.0000   60.0000 102

 54 omega   80.00  105.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   77.0000   90.0000 25

 55 omega   36.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000 -108.0000   78.0000 79

 56 omega   84.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   61.0000   30.0000 94

 57 omega   88.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   45.0000  -90.0000 90

 58 omega   80.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      110.0000   77.0000   60.0000 98
;
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0505923000
_diffrn_orient_matrix_UB_12      -0.0279764000
_diffrn_orient_matrix_UB_13      0.0522384000
_diffrn_orient_matrix_UB_21      -0.0666722000
_diffrn_orient_matrix_UB_22      -0.0805472000
_diffrn_orient_matrix_UB_23      0.0009012000
_diffrn_orient_matrix_UB_31      0.0203921000
_diffrn_orient_matrix_UB_32      -0.0121109000
_diffrn_orient_matrix_UB_33      -0.1268471000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            71755
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.417
_diffrn_reflns_theta_min         2.471
_diffrn_source                   'GV1000 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.557
_exptl_absorpt_correction_T_max  1.040
_exptl_absorpt_correction_T_min  0.708
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28a (release 18-03-2013 CrysAlis171 .NET)
(compiled Mar 18 2013,11:47:30)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.151
_exptl_crystal_description       plank
_exptl_crystal_F_000             1566
_exptl_crystal_size_max          0.3939
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.0656
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 5030 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.004(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     654
_refine_ls_number_reflns         11429
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0840P)^2^+0.6129P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    0.939
_reflns_Friedel_fraction_max     0.928
_reflns_number_gt                10908
_reflns_number_total             11429
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc45452e.txt
_cod_data_source_block           8b
_cod_original_cell_volume        4147.60(7)
_cod_database_code               7109851
_nottingham_internal_coll_name   GPRSCH
_nottingham_internal_coll_number 12456
_nottingham_internal_coll_client ER/RS
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_time '5 & 20'
_nottingham_internal_coll_frame_width 1
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_user   WL
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_user WL
_nottingham_internal_solution_user WL
_nottingham_internal_refinement_user WL
_nottingham_internal_validation_user WL
_nottingham_internal_validation_date 19/5/2013
_chemical_oxdiff_formula         'C19 H29 N O S'
_chemical_oxdiff_usercomment
'ERRSCF #12456 IN FOMBLIN FILM ON MICROMOUNT FOR ER/RS'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N39-H39 = N1-H1 = N20-H20
 0.91 with sigma of 0.02
 C48-C42 \\sim C48A-C42A \\sim C42-C44 \\sim C42A-C44A
 with sigma of 0.02
 C44-C45 \\sim C44A-C45A \\sim C48A-C47A \\sim C47-C48
 with sigma of 0.02
 C45-C46 \\sim C46A-C45A \\sim C46A-C47A \\sim C47-C46
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C42A \\sim C48A \\sim C43A \\sim C39A \\sim C44A \\sim C46A 
\\sim C45A \\sim C47A \\sim C41A \\sim C40A: 
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C39 \\sim C43 \\sim C47 \\sim C40 \\sim C42 \\sim C48 \\sim C46 
\\sim C44 \\sim C41 \\sim C45: 
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(C41A)=Sof(H41C)=
 Sof(H41D)=Sof(C42A)=Sof(C43A)=Sof(H43A)=Sof(H43B)=Sof(C44A)=Sof(H44C)=
 Sof(H44D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=
 Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=1-FVAR(1)
 Sof(C39)=Sof(H39B)=Sof(C40)=Sof(H40C)=Sof(H40D)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(C42)=Sof(C43)=Sof(H43C)=Sof(H43D)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=
 Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1A), C20(H20A), C39A(H39A), C39(H39B)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C21(H21A,H21B), C22(H22A,H22B), C24(H24A,H24B),
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B),
  C40A(H40A,H40B), C40(H40C,H40D), C41(H41A,H41B), C41A(H41C,H41D), C43A(H43A,
 H43B), C43(H43C,H43D), C44(H44A,H44B), C44A(H44C,H44D), C45(H45A,H45B),
 C45A(H45C,H45D), C46(H46A,H46B), C46A(H46C,H46D), C47(H47A,H47B), C47A(H47C,
 H47D), C48(H48A,H48B), C48A(H48C,H48D)
5.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C32(H32), C34(H34), C51(H51), C53(H53)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C57(H57A,H57B,H57C)
;
_shelxl_version_number           2013-2