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1 !"#$%&'()*,.//0"34 (C) C a Ts(C ) 3Ts a!"#$%&'()*,./0 ()*,. /0*,3. 567(8(9%&'():;<:= h h X Y RC a R' Me Ts R Me Ts RC R'./0/ h!"#$%&'()*, R 3 BF 4 BF 4 R R Ac Ac Ac Ac tertamine Ac Ac Ac Ac BF 4!"#$%& Bn Bn R Bn Bn Lewis acid Bn Bn Bn Bn KF Bn Bn F R Bn Bn nf, Ag 4 tertamine Bn Bn Bn Bn glycoside R Bn Bn Bn Bn Bn Bn Bn Bn R I(4,5) hosphatidylinositol 4,5bisphosphate from beef brain 3 I3 (Ins,4,53)!"#$%&'! Diacylglycerol (C. E. Ballou, 96)

2 YTETIC RBLEM. elective rotection and deprotection of six ydroxyl Groups. Effective ptical Resolution 3. Effective olyphosphorylation 4 5 myoinositol DmyoInositol,4,5trisphosphate RTECTI & RELUTI RYLATI R 4 R 5 R ( ) 3 XEA (bp 0 C/0.3 mmg) Exhaustive Bn Bn Bn Bn Bn ) Bn ) 3) mcba (Bn=benzyl) J. Chem. oc., erkin Trans., 99, R 3 R R (987) erich & Johns (987) Liskamp & van Boom (987) Bannwarth (988) FrasarReid (988) Dreef & van Boom for Ins (988) Vasella n synthesis elective Bn Bn? Bn RC R'C Bn R'' = (Bn)(), () R tetrazole R ybr 3 Br R Br (R) 3 (R=Bn, Me) ybr3 R' (R) 3Br R R R' R Br R'(R) mcba R R() monoesters R', tertamine R R' Br Br R'R, d/c R R' diesters Bn Bn Bn Bn (Me) Bn Bn ybr 3, 0 C C, 0.5h C 7 35 C C 7 35 C (Me) C 7 35 C C 7 35 C (Me) (.6 eq) 95% 85% (5 eq) ybr 3 y/c (:0) 0.5h, 0 C 94% Bn Bn Bn Bn Me (.4 eq) CR CR' to I() Bn Bn Me to I(4,5) C 35 C 7 C 35 C 7

3 catalyzed Ester Exchange & Fragmentation Bz axial equatorial. Amidite Bz Bz. mcba Bz Amidite Amidite.4 eq vs Bz Bz Bz Bz Bz Bz Bz Bz Bz Bz Bz Bz eq 0 64 : 48% X : 86% mcba M 7 6 hc (C)3h C h 4% 5% (C)3h 4% (C ) 3h 55% hc (nbu)3 (nbu) (C ) 3h nbu[(c ) 3h] % 36% 6% (C ) 3h 0% h(c ) 3 h(c ) 3 h(c ) 3 rt, h h(c ) 3 h(c ) 3 63% (C ) 3h (C ) 3h [h(c ) 3] 3 4% 4% h(c ) 3 85% 36% : Glycosylation based on (III) Chemistry (C ) n n= Tet. r (C ) n r r n=0 r r r! 4.95 ( J = z, 3 J = 8.7 z) Tet. = r = h(c ) 3 r r r r Bn Bn Bn (Me) X Bz Bn Bz Bz Bz X = F Tf El Cp Zr Ag 4 Cp f Ag 4 n Ag 4 Activator! 76% M4A, C % El (Me) R Bn Bn Bn Bz Bn Bz Bz Bz X = (Me) "! " ITf Zn Ag 4 MeTf 76% % 4 R i i Bn Bn (Me) Bn Bn I, Tf C, M 4A TID 45% (!=5%) BnBn Bn Bn TFA Me Bn Bn Bn (Me) Bn (Me) Bn Bn Bn Bn TID Me TID Bn Bn TMTf ybr 3, 3 Bn Bn C, M 4A 83% 74% 44% (diastereomer, 45%) Bn Bn Bn Bn C 7 35C Bn C Bn 7 35C Bn Bn. Mg 8% Bn Bn TID Me Bn Me Bn TID Bn. C Bn 7 35C Bn Bn C 7 35C 73% C 7 35C. nbu 4F3 89% hc. h, 3 89% 3., dc quant. IM Bn Bn Bn Bn (Me) ( n Bu) 3 Te 4 CD 3 h(c)3 M 4A, C Te Te4 Bn Bn Bn Te4: Zn: Bn % 9 (C)3h (!/") (97 : 3) 83 (5 : 49) Te Te 3 ( n Bu) Te 3 3 ( n Bu) 3 n Bu Te ( n Bu)

ynthetic methodologies based on on phosphite chemistry (Me)3 (. eq) Table!"#$%& xidant, (.0 eq) (.

4 53 Benzene 73 g(ac) (.) 0.5 90 80 TF 64 0.6 89 g(ac) (0.8) 64 C3C * 50 Fe 3 (.) 37 0.7 90 44 g (0.8) 6 0.8 93 Cu (0.8) 0.

8 75 olv: C various ways R R' R R' R R XR' R R R 3 (R) Te 3 Br LA R' Ester exchange R' Glycosylation Lewis acid (LA) R' Te4 mcba R'X y Br3 R'

4 ynthetic methodologies based on on phosphite chemistry (Me)3 (. eq) Table!"#$%& xidant, (.0 eq) (.4 eq) Me Me Table '($%& Table 3 )*$%& xidant (eq) Yield, % Equiv of Yield, % olvent Yield, % Te4 Te4 (0.8) 93 C 93 TeBr4 (0.8) Benzene 73 g(ac) (.) TF g(ac) (0.8) 64 C3C * 50 Fe 3 (.) g (0.8) Cu (0.8) *h(c ) 3 used b(ac)4 (0.8) olv: C olv: C various ways R R' R R' R R XR' R R R 3 (R) Te 3 Br LA R' Ester exchange R' Glycosylation Lewis acid (LA) R' Te4 mcba R'X y Br3 R' Exhaustive phosphorylation R' R R R' Redox phosphorylation elective phosphorylation a 3 natural I(5) Me a 3 permeable I(5) Me M rganogel 456' D h h Ac Ac diastereomixture L Me 0.5 wt% benzene EM pictures of xerogels D Ac Diastereo mixture [D:L]=5:5 [D:L]=4:6 [D:L]=3:7 Enantiomer Racemate [D]only [L]only [L:DR]=5:5

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5 a aq Benzene Gel Glass tube Water gelatin GelFolution hole remove 3 5 min.5 h After 30 min, take away 6';G 9.0 h 0 h D h h Ac Ac diastereomixture L!"#$%&'( IJKL5 MQR ;R TR UVWX \ )*, ] 6789:9; <=>345./0?@ABCDEFG5 345 ^!"#$%&'() Ala is he Val Me, 00 %, 00 % _J`abc def Q ml / min.f 89:;<=>:8?@!'!%!" 4 Me C3.0 eq. 3 min!%&% C C rn C,4Diaminobutylic acid (,4DA) is C,7Diaminoheptanoic acid (,7DA) C Arg C YZ[./0,[./0 [./0 Me!$ ( ' % " $ "! #!$ $!$ "$ )$ *,./0/34/56676 ABCDE!"#$%&' ()*))*) C 3,./0/ !"#$%&' ( )**, C3.!"#$%&' ( 7))*) C 3, MR (!"#$%&' ()*))*)) D CD 3 BCDE

Specification Details: Coded Dash Number M28803/1 -MC PART LISTINGS MANUFACTURER'S DESIGNATION OR TYPE NUMBER TEST OR QUALIFICATION REFERENCE

Specification Details: Coded Dash Number M28803/1 -MC PART LISTINGS MANUFACTURER'S DESIGNATION OR TYPE NUMBER TEST OR QUALIFICATION REFERENCE Specification Details: DLA Land and Maritime - VQ Date: 2/4/2015 Specification: MIL-DTL-28803 Title: Display, Optoelectronic, Readouts, Backlighted Segmented Federal Supply Class (FSC): 5980 Conventional: