A-13 H S SH 3 H H H H d. H HSH 4 I F F 5 H NH 3 d. 6 H H H H H H H 7 H H H d. H H H H H F H H d. H H H N H 3 H d. e. NH 4 f. N g. N h. N

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1 d Si S 10 6 N 5 P s 1 6 l HH HFd. l 1 7 Kl l 1 9 H H e. H F f. H 3 Li H 3 NH g. I l d. H 3 l h. H N H 1 10 LiH HF LiH 1 11 d H H H H H H H 1 15 H H NH NH H H d. e. H l f. HNH 1 16 H H l H H NH d. H N 1 17 l Nd. H 1 19 sp 3 sp 3 H sp 3 s l l l F F l I. l3. Hl 1. l. 3. HF d a d 1 l 4 l NH 4 H NH NH 4. Hl3. H 4. H 3 1. NH. 3. N 3 4. H H H H H H d. H NH 3 e. H 10 40, 15, 5, NH H 1 H H NH NH H H, NH, H 17 NH H F 18 H H P H H 19 1 F l I A-1

2 A-13 H S SH 3 H H H H d. H HSH 4 I F F 5 H NH 3 d. 6 H H H H H H H 7 H H H d. H H H H H F H H d. H H H N H 3 H d. e. NH 4 f. N g. N h. N l H H H H H 37 H NH 3 H NH H d. H S H n n 3 4 H H H n H H sec HH tert 3 5 HH HH H F H HI d. H e. NH H f. H H H H H H H 3 6 sec d. n e. f. sec 3 7 HH, 3 8 H HH H H H H HH HHH d. H H H H H HHH H H H 3 10,,4,,,5 d. 54,4 e. 3, 3f., H H H, HH d. HH

3 A H 4 1 H H H HH H 7 d. e. N f. H H 0 10 H d. 3,6 e. f sec 14d d H H H H H H H H 3 8 NH H H H H HH H H H H H H H H H H H H H l d d H H H H H HH H 4 7 I H H H l HPH H H H 4 8 Z 4 11 E Z 3,4 Z b d 4 14 a, c, f 4 16 a, c, f H H H H( ) 3 1 H 4 H 3 H H 4 1 l H H H 3 H H 4 0 R R 1,3 4 1 R R Rd. R S R Rd. S A,, E H H H

4 A-15 d A B D 4 39 BDF H H H H H H d. H HH H ,43 1d. 1,5 e. 143 f. 11,3 5 4 H H HNH A 5 1 H H H H H H 5 13 cis3,43 trans3 cis3 cis, a b b c n Dd. n Be. ndf. B ng. nb 5 0 G sec 6 4 H H H H H H HH H HH H HH H l F 6 5 H H 6 6 H H H H d. H H e. 6 7 H H H H d. H H H H H H H H f. H H H H HH H H H H H H d. H 6 15 RS RS , lh H H H H sp sp sp sp 3 spsp d. spsp 3 e. spsp f. sp sp g. sp sp 3 h. spsp 3 i. sp sp

5 A-16 6 H H d. H H 6 3 H H H H 6 4 H H H H H 6 5 H H H H H H H H H H H H H H H H H H H H Lindlar H H H H H H H H H H HH H H HH H H H Lindlar H Pd/ 7 9 H d. e. f e. lh H HH H NH H d. H 3 NH H f. l H HHH H l l H H HH HH l l H H l 7 4 / , HH H HH H,5,4,4 N H HH H 1,3 H HH H H 1,4

6 A H H H H H H N 8 3 1/ H H H H HH H H HH H3H 8 5 S R 3d d H H H l 8 11 H H H H H N ( ) 3 d. H SH 8 1 R 33S ab H H H H H H H H H H HH d. H H H H 3. E 8 0 tert tert 8 1 B B Bd. A d H H I H H I NH 3 NH 3 d. H DMS H EtH e. NH 3 NH 3 H /50 50 /50 terttert tert d. 31 e. 5 e., H H H H H,3 9 4 H3HHH3 H 33

7 A B 9 1 E 3,43Z 3, ,43 E 3, H 3 H 3 H H IR UV cm 1 8 µm H N d N sp H H H H 9 0 H N( ) N( ) 3 HH HH H H d. H BE 10 3 m/z H 1 6 H 1 5 H 10 d. 6 H 1 N 10 7, N( ) N( ) nm d. 3e. 3f TMS HH H 3 HH 3 H H l H H l H HH l

8 A , 13, B (H ) 4 (H ) 4 H d. 5 e. f. N,NN,N 11 4 B d H H R B A g H 3 NHd H H H H H H Mg Mg 1 10 R 33S B D 1 17 HH H H ( ) 3 H d. H H NH NH H NHH d. N H

9 A , 5, 6, 3, H 13 6 H H H H H H 13 7 H H H H H HH HH H H H H H H H H N H H H H H H 15 6 H H H H N H H H H N H Hl H H H BF 3 H H H BF 3 H N ABD 13 0 A D d. 5e. 5f D B H3 H H BuLi NHH H H NHH H H NH(H ) 4 NHH H NH(H ) 4 NHH H 16 1 DD D D L Ld. L 16 5 D

10 A D H 3 4 H 3 1 H D D ,4 1,4 1,6 d. H N AB AB AB 17 Ile d Asp Arg pi LAla DAlaLAsp DAspLGlu DGlu LAlaLAspLGlu Edman 17 GlyArgTrpAlaGluLeuMetProValAsp 17 4 HisLysLeuValGluProArgAlaGlyAla LeuGlySerMetPheProTyrGlyVal 17 6 LeuTyrLysArgMetPheArgSer NAM , 3, N1 N5 N H THF ,6 1,

11 A S N TGTTAGAG MetAspProValIleLysHis 1 7 MetAspProLeuLeuAsn GATGGAGTTATTAAAA HN N HN N N N H H N N H 1 14 A

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