Pure & Appi. Chem., Vol. 55, No. II, pp. 1749—1758, 1983. 00334545/83 $3.OO+O.OO Printed in Great Britain. Pergamon Press Ltd. ©1983 IUPAC

METAL ENOLATES IN

Teruaki Mukaiyama

Department of Chemistry, Faculty of Science, The , Tokyo 113, Japan

Abstract -Metalenolates play an important role in organic synthesis and in particular metal enolate mediated aldol type reactions provide very useful synthetic tools in stereoselec- tive and asymmetric carbon-carbon bond formations. Three types of metal enolate mediated aldol reactions developed in our laboratory are discussed.

During the past decade, generations and reactions of various metal enolates have been extensively studied and successful applications to the controlled formation of carbon-carbon bonds have been realized under mild conditions. Besides the well-studied based on lithium enolates, very versatile regio- and stereoselective carbon-carbon bond forming reactions have been established by the use of silyl enol ethers-Lewis acids, vinyloxy- boranes, and stannous e'iolates (Ref. 1). In this article, the chemistry of these three types of aldol reactions is discussed. They are: 1. The titanium tetrachloride promoted aldol reaction of silyl enol ethers. 2. Vinyloxyborane mediated aldol reaction. 3. The stannous enolate mediated aldol reaction.

I. THE TITANIUM TETRACHLORIDE PROMOTED ALDOL REACTION (Ref. 2)

Aldol reaction has long been recognized as one of the most useful synthetic tools and the reaction is usually carried out under basic conditions. However, under classical aldol reaction conditions in which basic media are employed, dimers, polymers, self-condensation products, or c,i3-unsaturated carbonyl compounds are invariably formed as by-products. Useful synthetic methods have been developed recently to alleviate those difficulties, especially under basic conditions, the lithio derivative mediated method offers one of the solutions to those problems (Refs. 1,3). On the other hand, there appeared no practical procedure for cross aldol reaction carried out under acidic conditions.

Enol ethers react with acetals or ketals by the promotion of Lewis acids to give aldol-type adducts. However, acid catalyzed reactions are often accom- panied with undesirable side reactions, when stoichiometric amounts of carbonyl compounds and enol ethers are employed (Ref. 4). The use of stoichiometric amounts of titanium tetrachloride, trimethylsilyl enol ether, and a carbonyl compound is a great advance in directed aldol reaction. Powerful activation of carbonyl groups by TiCl enables the nucleo- philic attack by trimethylsilyl enol ethers to form trimethylsilyl chloride and the titanium salt of the aldol-type product. In this case, undesirable dissociation of the adduct is inhibited by the formation of a stable titanium chelate, hydrolysis of which yields the desired -hydroxy ketone (Ref. 5). This type of reaction is also promoted by various other Lewis acids such as SnCl, BF3'OEt2, AlCl3, and so on. Among these acids, titanium tetrachloride was found to be superior to the other Lewis acids with respect to yields. The reaction proceeds with retention of the regiochemical integrity of the starting silyl enol ethers to afford the corresponding aldol regiospecifically. Starting enol ether compounds, silyl enol ethers, can be conveniently pre- pared regioselectively under either kinetically or thermodynamically control- led conditions.

1749 1750 T. MUKAIYAMA

TiC1

Me3SiOR3::=TiC14 RiR5

Enol ethers derived from ketones or aldehydes react with aldehydes at -73°C, whereas elevated temperatures are required for ketones. Although precise examination of the stereochemistry of the aldol products has not been done, this TiCl promoted reaction usually gives a mixture of threo and erythro isomers in comparable amounts.

Si(CH3)3 OH

+ TiCl4 -78°C Ph PhCH2CH2CHO

(threo : erythro=l :1)

Chemoselectivity is observed with acceptors having two different kinds of carbonly functions such as aldehyde and ketone or in the same molecule. Treatment of phenylglyoxal with enol ether 4 at -78°C affords the ct-hydroxy- y-diketone 5 (Ref. 5a).

1. TiCl4 C6H5COCHO +C6H5CH=C(CH3)[OSi(CH3)} 2 H C6H5COCHOHCH(C6H5)COCH3 20 5 4

The reaction of ketoesters other than g-ketoesters with the enol ether 6 gives hydroxyketoesters 7 as sole products (Refs. 5d,e). 1. TiCl4 CH3CO(CH2)CO2R +C6H5CH=(CH3)[OSi(CH3)3] n=0,2,3 6 2. H20 R=CH3, C2H5 CH3COCH(C6H5)C(OH) (CH3) (CH2)CO2R 2 Theadvantage of using acetals or ketals instead of aldehydes or ketones is that they act only as and probably coordinate with Lewis acids more strongly than the parent carbonyl compounds. Trimethylsilyl enol ethers react readily with acetals or ketals at -78°C in the presence of titanium tetrachloride to afford -alkoxy carbonyl compounds in high yields (Ref. 6).

OSi(CH 33 H 0 OR' + TiC14 R1-C=CR2R3 ,C(OR')2 —i R R1C-CR2R3-CR4R5

Varioussubstituted furanes are readily prepared by application of the TiCl- promoted reaction of ct-halo acetals with silyl enol ethers (Ref. 7).

Br BrR2RO 1 4 1 I OSiMe3 T1C14 I I Ry.R R -CHC(OCH3)2 + RCHC —> R-CHC-CH-C-R4 jL_j R2 R CH2C12, 00q toluene,ref1.2 R —78C,1--2 hr 58 hr Metal enolates in organic synthesis 1751

5-Alkoxy a,iB-unsaturated aldehydes such as 9 are valuable synthetic intermedi- ates because of their polyfunctionality. Reaction of acetals and the di- enoxysilane 8 in the presence of TiCl alone gives only polymers. However, the desired Ildehyde 9 is obtained in good yield by treating acetal and the silane 8 at -40°C in The co-existence of TiCh and Ti(O—<) (Ref. 8).

DBU > ,0CH3 TiClTiO1Pr)4%,%5\J3

______DBU

73% 84% This method has been used successfully in the synthesis of natural products such as vitamin A, variotin and hypacrone (Ref. 9). Thus the titanium tetrachloride promoted aldol reaction offers a very valuable approach to aldol adducts under mild conditions. In particular, it has realized the utility of silyl enol ethers as isolable and useful enolate equivalents and the acidic medium permits the use of base sensitive functional groups in aldol type reactions which do not survive lithiated derivative mediated methods.

2. VIYNLOXYBORANE MEDIATED ALDOL REACTION

Ten years ago we found that the vinyloxyborane derivative II was formed in reaction of phenyl di-n-butylthioboronite lOwith ketone. Similarly, vinyloxy- borane 12 was prepared by the reaction of thyl vinyl ketone with phenyl di-n-butylthioboronite (Ref. 10).

Bu B-SPh + — 2 CH2=C=O CH2=C u2 CH3 Bu B-SPh + CH=CH-COCH -____PhSCH,CHC 2 2 . u2 i_p

Wehave pointed out as a first example that these vinyloxyboranes are highly useful synthetic intermediates to react with various carbonyl compounds to afford-hydroxycarbonyl compounds in excellent yields under essentially neutral conditions (Ref. 11). Forexample, treatment of vinyloxyborane 13 with benzaldehyde at room tempera- ture for 10 minutes gives crossed aldol 14 in 98% yield. This method is a typical example of an aldol reaction cariTed out under neutral conditions (Ref. 10).

1.PhCHO n-C4H9CH=C(C6H5)OB(C41-19)2 PhCH(OH)C4H9CHCOPh 2112O 1 98%

Alternatively, it had been known at that time that vinyloxyboranes could be prepared by reaction of a diazoketone 16 with a trialkylborane 15 (Ref. 11), or by the 1,4-addition of an alkylborane to an a,iB-unsaturated kitone 15 (Ref. 12). The reaction of enolizable aldehydes with a 4-dialkylboryloxy-2- isopropyl-6-methylpyrimidine 18 also gives vinyloxyboranes (Ref. 13). 1752 T.MUKAIYAMA

BuB +NCHCOX —- BuCH=C OBBu 16 2 CH CH =CHCOCH + BuB ______>BuCHCH=C 2 3 3 2 OBBU

R1R2CHCHO BR3 + R1R2C=CHOBR2

More recently, it was found that a boron enolate of an ester was generated by treatment of ethoxyacetylene 19 with mercury(ll) acetate and diphenylboronic acid (Ref. 14).

EtOCCH + Hg(OAc)2— EtO Ph2BOH PhB0C=CH2 ig 20

A convenient method for generation of vinyloxyboranes from a wid variety of enolizable ketones has been reported. Dialkylboryl trifluomethanesulfonate (R2BOTf) reacts with ketones in the presence of a tertiary amine to produceS vinyloxyboranes. The vinyloxyboranes thus generated react with aldehydes to give crossed aldols in high yields (Ref. 15).

OBR2 '. RCHO R BSO CF 11 2 1 2 3 - RC=CHR R COCH(R )CHOHR R1COCH2R2 Tertiary amine 2. H20

Regioselective generation of vinyloxyborane is readily controlled by a suitable combination of reagents. For example, the reaction of 4-methyl-2- pentanone with dibutylboryl trifluoromethanesulfonate and diisopropylethyl- amine produces the kinetically controlled vinyloxyborane 21 which then reacts with an aldehyde to afford the 8-hydroxyketone 22 (Ref. lt).

n-Bu2BSO3CF3 ?B(C4H9)2 1. RCHO i-C3H7CH2COCH3 i-Pr NEt 3H7CF12C12 —i-C3H7CH2C0CH2CH0HR 2 2•2 H

In contrast, the thermodynamically stable vinyloxyborane is generated by the reaction of the ketone and 9-borabicyclo [3.3.lJ-9-nonanyl trifluoromethane- sulfonate (9-BBN-) in the presence of 2,6-lutidine at -78°C for 3 hours. Subsequent reaction with an aldehyde gives the corresponding aldol 23 (Ref. l5a).

— R CH2COCH3 R1CH=C(CH3)O RCH(COCH3)CHOHR 2, 6-lutidine This reaction proceeds under very mild conditions without causing isomeriza- tion of double bond of ,y-unsaturated aldehydes. Thus '-ionon is synthesized without any contanination with isomeric ct- and 13-ionones by a cross aldol reac- tion of vinyloxyborane with y-citral (Ref. 16).

BU2BOSO2CF3 ,Et3N CH3&H3 Metal enolates in organic synthesis 1753

The most important stereochemical question in the directed aldol reaction concerns the formation of threo and/or erythro isomers of aldols or ketols. Consequently, extensive stereochemical studies on the geometry of enolate species, the nature of the metal, kinetic vs. thermodynamic control, and have been carried out.

Under kinetically controlled conditions the formation of stereoisomers is dependent on the geometry of the starting enolate. In general, the (Z)- enolate gives the erythro isomer and the (E)-enolate gives the threo isomer.

OM OOH Rn' +RCHO— 'TR R2 E threo

O OH RCHO R' -' R R2 [H4L] erythro

The carbonyl component approaches the enolate perpendicularly, and the reac- tion proceeds via a pericyclic process.

Dialkylboron enolates have relatively short metal- and metal-oxygen bonds, which is suited for maximizing l,3-diaxial R-L interactions in the transition states. Thus facilitating the formation of more stable transition states 25 and 26 where R occupies a pseudoequatorial position, the vinyloxy- boranes undergo stereoselective aldol reaction (Ref. llb). The vinyloxy- borane generated in situ from 3-pentanone and 9-borabicyclo {3.3.lJ-9-nonyl- trifluoromethanesulfonate (9-BBN triflate) by the action of 2,6-lutidine reacts with benzaldehyde in a complete stereoselective manner, giving erythro aldol 27, almost exclusively (Ref. 15a).

9-BBN triftate PhCHO -. (C2 H5)2C0 2,6-Lutidine C2H5 C2H5CO OH

Further study of stereodefined vinyloxyborane condensation reactions by D. A. Evans and S. Masamune revealed that the (Z)—isomers react with various aldehydes to yield predominantly the erythro aldols, whereas the (E)—isomers react somewhat less stereoselectively to give threo aldols as the major products. In some cases the preparation of either (E)-vinyloxyborane or (Z)— vinyloxyborane in a highly stereoselective manner can be achieved starting from the same ketone, resulting in a stereoselective synthesis of either erythro and threo aldol (Refs. 17, 15b,c,f). 1754 T. MUKAIYANA

Furthermore, Evans (Ref. 18) and Meyers (Ref. 19) recently showed enantio- selective aldol reactions using chiral boron enolates.

C Me

I Me Me R R R2O('R CO2Me CO2Me HO OH

Vinyloxyboranesprepared under very mild conditions allow aldol type reac- tions essentially under neutral conditions. Acyclic stereoselection which is a challenge among many organic chemists has been achieved by employing vinyloxyborane mediated aldol reaction. This method is applied extensively to the synthesis of natural products.

3. THE STANNOUS ENOLATE MEDIATED ALDOL REACTION

The chemistry of tin(IV) enolates has been studied recently andseveral inter- esting features of these species have been explored (Ref. 20),whereas tin(ll) analogues (stannous enolates) are relatively unkown species insynthetic in part for lack of general preparation methods. Recently we found that stannous(ll) enolates could be prepared in situ by the oxidation addition of o-bromoketones to metallic tin (Ref. 21).

It was reported that the enolate was regioselectively generated by the coupl- ed attack of dialkylaluminum chloride and on a-bromoketone and that the aldol is produced in a regioselective manner, however, diastereoselectivity is generally low. Stannous enolates generated from o-bromoketones and Sn(0) react with aldehydes in a highly regioselective manner with high erythro selectivity (Ref. 21c).

OSnBr OOH R1 ______>R1 RCHO 6399 (erythro:threo9O.iO946)

Moreconveniently, stannous enolates can be generated by the reaction of ketones and Sn(OTf)2 in the presence of a tertiary amine. In this reaction, the choice of the tertiary amine is crucial. For example, , or DBU which can coordinate strongly to divalent tin failed to promote the reaction, while N-ethylpiperidine gave an excellent result. These divalent tin enolates undergo aldol reactions to give -hydroxy ketones in good yields, under extremely mild conditions where good to excellent erythro selectivity is observed (Ref. 22). Metal enolates in organic synthesis 1755

0 Sn(0Tf)2+Q R"CHO H20 0 OH 0 OH Et RCH2R' R"'' R" + R" CH2CL2-78°C,05h 25h erythro threo 71-86% (erythro : threo=86 : 14->95 :5)

Moreover, the stannous enolates generated by the above procedure are highly reactive and can react even with ketones to give ketone-ketone cross coupling products in good yields (Ref. 23). Boron enolates, which are very versatile metal enolates display poor reac- tivity toward ketones and more nucleophilic lithium enolates react with less hindered ketones in moderate yield. Considering the reactivities of those enolates, we would like to emphasize the high reactivity of stannous enolates. Also noteworthy is the fact that employment of aromatic ketones as acceptor enhances threo selectivity.

Sn(OTf)2+Q R2R3 t ? OHR3 RCCH2R1 R2 CH2Ct23O°C15min R1 R R=Ph,RCH3, R2=Ph, R3=CH3 60% (100% threo)

-Hydroxy aldehydes and 13-hydroxy derivatives are very useful synthetic building blocks. In particular g-hydroxy aldehydes are utilized for the construction of a variety of polyoxygenated natural products.

3-Acylthiazolidine-2-thiones prepared from acyl chlorides and thiazolidine-2- thione or from carboxylic acids and thiazolidine-2-thione by DCC or pyridinium salts as condensation reagents undergo a similar aldol type reaction to give g-hydroxy carbonyl compounds in excellent yields with high erythro selectivity. This type of crossed coupling products are very versatile synthetic materials and can be transformed into , , aldehydes, diols, respectively in good yields (Ref. 24).

Sn(OTf)2 R'CHO RNS +R'N5 Et-N,CH2CL2 R" —78°C erythro threo

97:3) 1756 T.MUKAIYAMA

3 eq 9Ho K2C03 MeOH orEtOH, PhçOM e#.s95O/ yield r.t. (Et)

1) 900/o yield .SiC1/

toluene,—76°C 65°tyietd 1)NaBH4I qucint. OH OH 2)H4 L ,

Tran8-a,13-epOXyketOnes are usually prepared by hydrogen peroxide epoxidation of a,i3-unsaturated ketones, whereas cis-isomers cannot easily be prepared. The mildness of the present aldol reaction provides a stereoselective syn- thesis of cis--substituted-cL,3-epoxyketones. Aldol reaction between an a.- bromoketone and an aldehyde followed by KF-dicyclohexyl-18-crown-6 tretment gave cis-epoxyketones stereoselectively (Ref. 25).

Br Br R1 Sn(OTf) R2CHO R1 I R2R1 R2 Br bass + 0 0 OH 0 OH Syn Anti base base

RL(\2R)/A%2 °Cis Trans

Afacile synthesis of the branched chain sugar, 2-C-methyl-DL-lyxofuranoside has been achieved by using the tin(ll) enolate of l,3-dihydroxy-2-propanone derivative and methyl pyruvate (Ref. 26).

0 0 OH 0 II Sn(OTf)2 + CJ CHJCCO2CH3 ROCH2 \,,3IICH3 ROC H2C H2OR COCH3 CH2Ct2 OR anti J Metal enolates in organic synthesis 1757

CH3 RO0Et I ROORO OHL 610 RO OH '° RO OH N. CH CH >98:2). 851o\ ,.. :i3=1:1) '(H)OEt (H)OEt RO v HO R PhCH2- RO OH 91% HO OH

(one onomer) (one onomer)

(i)Li(s-Bu)3BH (ii) Dibal (iii) EtOH/H4 (iv) KOtBu, excessEU(v)H2/5%Pd-C Although several asymmetric aldol reactions have been reporte.d recently, groups are usually attached to the ketone equivalent mole- cules in these reactions. No example existed so far in aldol type reaction where two achiral carbonyl compounds are used for constructing a chiral mole- cule with the aid of a ligand. Based on the considerations that divalent tin having vacant d orbitals, is capable of accepting a bidentate ligand coupled with the fact that (S)- derived chiral diamines are efficient in certain asymmetric reactions, enantioselective aldol reaction via divalent tin enolates with chiral diamines was explored. A highly enantioselective cross aldol reaction between aromatic ketones or 3-acetylthiazolidine-2- thione and various aldehydes has been achieved, in which chiral diamines derived from (S)-proline worked very effectively as ligands. This is a first example for the formation of cross aldol in high optical purity starting from two achiral carbonyl compounds employing chiral diamines as chelating agents (Refs. 27,28).

PhC2H5 Sn(OTt)2 ______PhCHO PhPh EtQCC Me —78°C (75-90% ee) (Sn(OTf)2:N-ethylpiperidine:propiophenone:chiral diarnine:benzaldehyde =1.0:1.15:0.8:1.2:1.2)

os (NTh OHO S CH-r1's Sn(OTf)2 >Me L.,) RCHO R--NS -95°C Et-N (65-90% ee) CH2C2,-7B°C Sn(OTf)2:N-ethylpiperidine:chiraldiamine:3-acetylthiazolidine-2-thione:aldehyde =1.0:1.2:1.2:0.85:1.15.

These compounds derived from 3-acetylthiazolidine-2-thione are very versatile chiral materials, capable of being transformed into various synthetic inter- mediates as demonstrated before (Ref. 28). Thus the characteristic features of tin(ll) enolates enable the stereoselective synthesis of aldol products even from two different ketones. Combination of Sn(OTf)2 and N-ethylpiperidine provides an easy approach to tin(ll) enolates, whereas tin(IV) enolates have been prepared through relatively laborious multi step procedures. Enantio- selective aldol reaction effected by chiral diamines also enhances the utility of tin(ll) enolate as versatile synthetic intermediate. It is highly expected that tin(ll) enolates will find useful applications in organic synthesis. cL1 'L VNVAIVXI1W

SDNHJHdI

'1 SMOIAOI (17) 'L'V UOSIOTM PU 'f'M 'U171T1fl0H ''O '1 '91 1 '(8961) (q) 'O'H 'GsnOJ-J uJOPOW,, 3T0UXg 'SUOT317aH 'V'M 'UTUt17A10 °1W ')td 'V) 'dd 689-6Z9 '(ZL6I) (3) 'J '17U[17i(TIflN ''0 '2I '8Z £OZ '(z861) 'Z IOd MOTAOJ 'J '17U117A117)IflN 'C7i3Uy ''W3 'UI 'p.j L18'9L'V3UV '(6L61) '5 'J U17 'H 'T0I 'ci6u ''Wj3 'UI 'p '2U 'L '(s961)j '17 '0 101ST U17 'd 'LO '171 511 'd (17) '10PflTPS 'a7y 'O '(5961J (q) '1o1oquojjj '(rl6uy ''WL3 'U '7 '2Du '8 55 '(6961) ' (17) 'J 'uIAT)[fl14 ') 'OUU1J PU 'N '1SmxN 'f 'WJ? 'wailo 'OOg '96 £OSL '(17L61) (q) ' 'mATnN 'N ')smxN pU ')I 'OUU1Z5 'Wdi3 11O1''l '(sL6I) () ' ouucj pu 'j 'rnuXin14 '-n 'wat 'oog udp '617 £5171 'j 'j -E)nj1 117L ')i (9L61) ' (p) ouu pu 'ux 'Wi3 ''LL'[ 1(5L61) () 'OUu15 '-flg 'Wz3 'oog 'udp '617 V8ZZ '(9L61) '9 'J WAI)[fl14 'N 'TqSk 'WZj3 S1''4I '(vL61) 'L 'I 'IIN 'H '[T'TI pu 'N 'WOUJ 'WjQ "74d7 LZS '(sL6I) '8 () 'I U11AT)[flV1 'V 'tpT14SI 'Wi1O 61S"74T '(LL6I) (q) 'V piqs 'J 'T)[fl4 '7fl 'Wt3 'o 'udp '05 1911 '(LL6I) () 'V pns DU 'J 'rnuXi[fl14 'Wij3 ''i[ L911 '(ILL6T) 6 (is) 'L rnilAT)[nN 'V 'pi{SI "iO 10Z1''74T '(sL6I) (q) 'V piqsj pu 'j 'u1ATtnFI L9V"Pq '(LL6I) () 'V pnjsj pu 'j 'urikn14 'n& 'wi3 'oog 'UP '15 LLOZ '(8L61) (p) 'A 'i1TSkH '14 'MZTqSTN pu 'j 'U)]B 'WZ3 L85''4U '(5L61) 'oi () 'i 'urXiin '>1 'wouj pu ' 'r' 'r 'WV 'Wi13 '°°S 'S6 L96 '(5L61) (q) 'i 'uioui 'w 'xnw pu 'L 'iwketn 'ng 'waiLo 'dos 'udp 'w 'i 'j )[fl14 '9V L081 (5L61) ' (3) ''nw 'tuiouj pu 'w 'pqi —'i oo. (sL61) '11 () '1 ZOOn pU '5 'O)[UTJ 'p 'WV W9 'oog '06 9565 '(8961) (q) 'pq '06 1689 '(8961) (3) r Z0014 pu 'rj ' 'f'UUfl WaZQ ''OO' 'WZ3 'UflWWOQ 651 (6961) (p) 'wp'i. jj mx uoop 'r sstc (6961) (o) 'wap' f 'WV WaiW '°S '16 5619 (6961) Z1 () 'V 'flZfl5 'J 'OS1cf •H J 'OOUflS ' 'qOj 3H 'UMO1 14'N 'TO}J M'U 'oqv>i r 'WT/ wdzW os 'i 8OLS '(L961) (q) j' 'uMoi '[OI p4'J 'fl.}J P11 M) ')[p3q 'pq '68 60L5 (L961) () 'M') '3' 'UMOJ5 \J 'P[flZflS 'S 'U1UO14 'T)[11kJ'\r piie '14 'T4OJ 'Pq 'Z6 'ZIL 171L (oL61) 1 'M '1ZUOJ H 'P1S0N PU }J '1OSç)J SflLSflf qdt7 UUV wai3 OL1 (9L61) 171 [\J IflJJ pu J 'EuVAT)tflN 'wzj (z861) S1 LL J -ng L1 (o861) (q) () OnOU pU ' og ud 's rij 'SUA[ J '1A PU A'f 'UOS1N f LLf WZO os '[01 0Z19 (6L61) pu s 'unusi v,ij uotp szzz'r j61) (p) L WAT)[flN PU L 'flOU WZ1D 6SS''q3[ (9L61) () 'j 'nouj j 'nirnuiq PU L 'wArinvi si'pq (6L6T) U) •EVG UA UJOH PU •S 'OUflU1S1 UOdDtJ 6ZZZ'[ (6L61) •9I: L N '°S '0 'MZ1L •wailo 'r oi (9L61) L1 'UflUIS S 'T1ON A'G 'UIOH pU 1Q S)OO1 uopvczL2; ' S991 (6L61) . . 'Q 'SUA f 'S11 J'J 'UT-IS f WTf •Wi13 °S 'SOT LZIZ (1861) 61 J\T SJOAO 'OOuFW f Wf Uj3 S 'OI 8LZ17 (iii) oz s io; idurx () X 'o:ouieurEx H 'T1E:1A 'rnFcAn1N .r .wz13 '00S •wa3 'UflWWO3 Z91 (1861) (q) •s IAUqS pife ç 'IIT:S -v(IaL uozp •;L7 ':z LZ9 (z861) r £ZL • •i iz () g poig pu j 'wAin wa ' (1861) (q) P1H PU •L 'WATIflN '•piqi 191 (z861) (D) 'L P1H pu •J L9V . •pqi ' (z861) •zz •j 'sui pu N 'MsMI uiazio '•:r (z861) Z M1 suos pilE 'J 'rnuXT)InN wo '•T 6S171 (z861) '17Z M MSMJ PU L 'wATin wazio 'LLar £601 (z861) 1091 SZ L 'rnLURi(-[)tnN J 'H pu N 'MESMJ 'wz ''aj (z861) 9Z ]J SUA pu d 'TN •Wi13 'I S6S (86I) LZ N MSMJ PU •I 'uAT)1n wai '•ai 117171 (z861) 8Z N MSMI J 'A1fl WLj3 ''l L6Z (s6T)