Biomimetic Total Synthesis of the Pentacyclic Amaryllidaceae Alkaloid Derivative Gracilamine.
Gao, Nadia Yuqian; Banwell, Martin G.; Willis, Anthony C.; Organic letters 19 (2017) 162–165; doi:10.1021/acs.orglett.6b03465

data_1544940
_publ_section_title
;
 Biomimetic Total Synthesis of the Pentacyclic Amaryllidaceae Alkaloid
 Derivative Gracilamine.
;
_journal_issue                   1
_journal_name_full               'Organic letters'
_journal_page_first              162
_journal_page_last               165
_journal_paper_doi               10.1021/acs.orglett.6b03465
_journal_volume                  19
_journal_year                    2017
_chemical_compound_source        local
_chemical_formula_moiety         'C37 H52 N2 O8 S1 Si1'
_chemical_formula_sum            'C37 H52 N2 O8 S Si'
_chemical_formula_weight         712.98
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             16-05-31
_audit_creation_method           CRYSTALS_ver_14.40
_audit_update_record
;
2016-05-31 - Report on C37 H52 N2 O8 S Si 
             by Anthony C. Willis
             for   Nadia Gao and Martin Banwell

2016-05-31 - details of refinement in _refine_special_details below

2016-05-31- passes checkcif tests with minor warnings  
;
_cell_angle_alpha                78.5156(13)
_cell_angle_beta                 86.0516(12)
_cell_angle_gamma                75.7746(12)
_cell_formula_units_Z            4
_cell_length_a                   10.6659(1)
_cell_length_b                   12.3000(2)
_cell_length_c                   29.9835(5)
_cell_measurement_reflns_used    23435
_cell_measurement_temperature    150
_cell_measurement_theta_max      72
_cell_measurement_theta_min      4
_cell_volume                     3735.77(10)
_computing_cell_refinement       'CrysAlisPro (Agilent Technologies, 2015)'
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
;
_computing_data_reduction        'CrysAlisPro (Agilent Technologies, 2015)'
_computing_molecular_graphics    'PLATON (Spek, 2008)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'Supernova (Cu) X-ray Source'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.031
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            59407
_diffrn_reflns_theta_full        71.405
_diffrn_reflns_theta_max         72.504
_diffrn_reflns_theta_min         4.277
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.507
_exptl_absorpt_correction_T_max  0.97
_exptl_absorpt_correction_T_min  0.90
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       lath
_exptl_crystal_F_000             1528.000
_exptl_crystal_size_max          0.274
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.021
_refine_diff_density_max         0.82
_refine_diff_density_min         -0.48
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.0000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     927
_refine_ls_number_reflns         14724
_refine_ls_number_restraints     47
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0466
_refine_ls_shift/su_max          0.0077398
_refine_ls_shift/su_mean         0.0001269
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.05P)^2^ + 2.74P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1188
_refine_ls_wR_factor_gt          0.1142
_refine_ls_wR_factor_ref         0.1188
_reflns_limit_h_max              13
_reflns_limit_h_min              -13
_reflns_limit_k_max              15
_reflns_limit_k_min              -14
_reflns_limit_l_max              36
_reflns_limit_l_min              0
_reflns_number_gt                12947
_reflns_number_total             14724
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.36
_oxford_diffrn_Wilson_scale      0.15
_oxford_refine_ls_r_factor_ref   0.0526
_oxford_refine_ls_scale          2.609(15)
_oxford_reflns_number_all        14724
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title
'Z:\ban1633SN\Tony_ban1633SN_data At 16:28 on'
_cod_data_source_file            ol6b03465_si_007.cif
_cod_data_source_block           ban1633SN
_cod_depositor_comments
'Adding full bibliography for 1544938--1544940.cif.'
_cod_original_sg_symbol_Hall     '-P 1 '
_cod_original_sg_symbol_H-M      'P -1 '
_cod_database_code               1544940
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, C(1,U'S) UNTIL C(84) 
CONT C(85,U'S,OCC) UNTIL C(88) 
CONT S(89,U'S) UNTIL O(99) 
CONT C(185,U'S,OCC) UNTIL C(188) 
CONT C(122,OCC,U[ISO]) UNTIL  C(125) 
FIX C(122,U[ISO]) UNTIL  C(125) 
EQUIV C(22,OCC) UNTIL C(25)  C(122,OCC) UNTIL C(125) 
WEIGHT -1  C(122,OCC) UNTIL C(125) 
EQUIV C(85,OCC) UNTIL C(88)  C(185,OCC) UNTIL C(188) 
WEIGHT -1  C(185,OCC) UNTIL C(188) 
EQUIV C(86,U[11]) C(186,U[11]) 
EQUIV C(86,U[22]) C(186,U[22]) 
EQUIV C(86,U[33]) C(186,U[33]) 
EQUIV C(86,U[12]) C(186,U[12]) 
EQUIV C(86,U[13]) C(186,U[13]) 
EQUIV C(86,U[23]) C(186,U[23]) 
RIDE N(11,X'S) H(111,X'S) 
RIDE N(61,X'S) H(611,X'S) 
RIDE O(49,X'S) H(491,X'S) 
RIDE O(99,X'S) H(991,X'S) 
RIDE C ( 2,X'S) H( 21,X'S) 
RIDE C ( 5,X'S) H( 51,X'S) H( 52,X'S) 
RIDE C ( 8,X'S) H( 81,X'S) 
RIDE C ( 10,X'S) H( 101,X'S) 
RIDE C ( 13,X'S) H( 131,X'S) 
RIDE C ( 14,X'S) H( 141,X'S) 
RIDE C ( 15,X'S) H( 151,X'S) H( 152,X'S) 
RIDE C ( 16,X'S) H( 161,X'S) 
RIDE C ( 18,X'S) H( 181,X'S) H( 182,X'S) 
RIDE C ( 19,X'S) H( 191,X'S) 
RIDE C ( 21,X'S) H( 211,X'S) 
RIDE C ( 22,X'S) H( 221,X'S) H( 222,X'S) 
RIDE C ( 23,X'S) H( 231,X'S) 
RIDE C ( 24,X'S) H( 241,X'S) H( 242,X'S) H( 243,X'S) 
RIDE C ( 25,X'S) H( 251,X'S) H( 252,X'S) H( 253,X'S) 
RIDE C ( 29,X'S) H( 291,X'S) H( 292,X'S) 
RIDE C ( 30,X'S) H( 301,X'S) H( 302,X'S) H( 303,X'S) 
RIDE C ( 33,X'S) H( 331,X'S) H( 332,X'S) H( 333,X'S) 
RIDE C ( 34,X'S) H( 341,X'S) H( 342,X'S) H( 343,X'S) 
RIDE C ( 36,X'S) H( 361,X'S) H( 362,X'S) H( 363,X'S) 
RIDE C ( 37,X'S) H( 371,X'S) H( 372,X'S) H( 373,X'S) 
RIDE C ( 38,X'S) H( 381,X'S) H( 382,X'S) H( 383,X'S) 
RIDE C ( 43,X'S) H( 431,X'S) 
RIDE C ( 44,X'S) H( 441,X'S) 
RIDE C ( 46,X'S) H( 461,X'S) 
RIDE C ( 47,X'S) H( 471,X'S) 
RIDE C ( 48,X'S) H( 481,X'S) H( 482,X'S) H( 483,X'S) 
RIDE C ( 52,X'S) H( 521,X'S) 
RIDE C ( 55,X'S) H( 551,X'S) H( 552,X'S) 
RIDE C ( 58,X'S) H( 581,X'S) 
RIDE C ( 60,X'S) H( 601,X'S) 
RIDE C ( 63,X'S) H( 631,X'S) 
RIDE C ( 64,X'S) H( 641,X'S) 
RIDE C ( 65,X'S) H( 651,X'S) H( 652,X'S) 
RIDE C ( 66,X'S) H( 661,X'S) 
RIDE C ( 68,X'S) H( 681,X'S) H( 682,X'S) 
RIDE C ( 69,X'S) H( 691,X'S) 
RIDE C ( 71,X'S) H( 711,X'S) 
RIDE C ( 72,X'S) H( 721,X'S) H( 722,X'S) 
RIDE C ( 73,X'S) H( 731,X'S) 
RIDE C ( 74,X'S) H( 741,X'S) H( 742,X'S) H( 743,X'S) 
RIDE C ( 75,X'S) H( 751,X'S) H( 752,X'S) H( 753,X'S) 
RIDE C ( 79,X'S) H( 791,X'S) H( 792,X'S) 
RIDE C ( 80,X'S) H( 801,X'S) H( 802,X'S) H( 803,X'S) 
RIDE C ( 83,X'S) H( 831,X'S) H( 832,X'S) H( 833,X'S) 
RIDE C ( 84,X'S) H( 841,X'S) H( 842,X'S) H( 843,X'S) 
RIDE C ( 93,X'S) H( 931,X'S) 
RIDE C ( 94,X'S) H( 941,X'S) 
RIDE C ( 96,X'S) H( 961,X'S) 
RIDE C ( 97,X'S) H( 971,X'S) 
RIDE C ( 98,X'S) H( 981,X'S) H( 982,X'S) H( 983,X'S) 
RIDE C(86,X'S) H(861,X'S) H(862,X'S) H(863,X'S) 
RIDE C(87,X'S) H(871,X'S) H(872,X'S) H(873,X'S) 
RIDE C(88,X'S) H(881,X'S) H(882,X'S) H(883,X'S) 
RIDE C(186,X'S) H(1861,X'S) H(1862,X'S) H(1863,X'S) 
RIDE C(187,X'S) H(1871,X'S) H(1872,X'S) H(1873,X'S) 
RIDE C(188,X'S) H(1881,X'S) H(1882,X'S) H(1883,X'S) 
RIDE C ( 122,X'S) H( 1221,X'S) H( 1222,X'S) 
RIDE C ( 123,X'S) H( 1231,X'S) 
RIDE C ( 124,X'S) H( 1241,X'S) H( 1242,X'S) H( 1243,X'S) 
RIDE C ( 125,X'S) H( 1251,X'S) H( 1252,X'S) H( 1253,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
DIST 1.89, .02 = SI(82) TO C(85), SI(82) TO C(185) 
DIST 1.54, .02 = C(85) TO C(86), C(85) TO C(87), C(85) TO C(88) 
DIST 1.54, .02 = C(185) TO C(186), C(185) TO C(187), C(185) TO C(188) 
ANGLE 110 2 = SI(82) TO C(85) TO C(86),  SI(82) TO C(85) TO C(87) 
CONT  SI(82) TO C(85) TO C(88) 
ANGLE 110 2 = SI(82) TO C(185) TO C(186),  SI(82) TO C(185) TO C(187) 
CONT  SI(82) TO C(185) TO C(188) 
ANGLE 110 2 = C(86) TO C(85) TO C(87),  C(86) TO C(85) TO C(88) 
CONT  C(87) TO C(85) TO C(88) 
ANGLE 110 2 = C(186) TO C(185) TO C(187),  C(186) TO C(185) TO C(188) 
CONT  C(187) TO C(185) TO C(188) 
REM 
U(IJ) 0.0, .02 = C(85) TO C(185) 
REM U(IJ) 0.0, .001 = C(86) TO C(186) 
U(IJ) 0.0, .02 = C(87) TO C(187) 
U(IJ) 0.0, .02 = C(88) TO C(188) 
REM 
LIMIT 0.001 C(86,U[12]) 
REM 
DIST 1.54, .02 = C(12) TO C(122) 
DIST 1.54, .02 = C(122) TO C(123) 
DIST 1.54, .02 = C(123) TO C(124) 
DIST 1.54, .02 = C(123) TO C(125) 
ANGLE 110 2  = C(12) TO C(122) TO C(123) 
ANGLE 110 2  = C(122) TO C(123) TO C(124) 
ANGLE 110 2  = C(122) TO C(123) TO C(125) 
ANGLE 110 2  = C(124) TO C(123) TO C(125) 
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                    
;