A. Hydrogenation of Alkenes (and Aryls) B. Formation of Aryls
C. Alkylations and Arylations of Alkenes
D. Conjugate Reduction of Conjugated Aldehydes, Ketones, Acids, Esters and Nitriles E. Conjugate Alkylations
F. Cyclopropanations, including halocyclopropanations
SECTION 74A: Hydrogenation of Alkenes (and Aryls) Reduction of aryls to dienes are listed in Section 377 (Alkene-Alkene).
Jso2ph
[ (t-Bu2Ph)PdPt-Bu]2 / 02 w
TfEH2
Cho, 1.S .; AIPer. H, J. Org. Chem., 1994, 59, 4027
Section 74A Hydrogenation of Alkenes 73
“colloidal palladium”
Hz, ether, 25OC
“colloidal palladium” = [TMS(OSiHMe),OTMS]Pd(hfacach
Fowley, L.A.; Michos, D.; Luo, X.-L.; Cr;ibtree. R& Tetrahedron Mt., 1993, 34, 3075 chirti catalyst, H2, 65OC
Ph Ph
91% (>99% ee) Broene, R.D.; Buchwald. SL, .I. Am. Chem. Sot., 1993, 115, 12569
Hz, rt , lh , MeOWH20
RuC13, TOA
TOA = trioctylamine 99%
(ciskans = 1.5) Fache, F.; Lehuede, S.; LeMaire. M, Tetrahedron Lett., 1995, 36, 885
[ (t-Bu2PH)Pd(Pt-Bu)2]2, H2 ,02 Ph THF/CH2C12,6h
0
Cho, I.S.; Lee, B.; m Tetrahedron Lett., 1995, 36, 6009
aq. Ba(OH), , NiAl(Raney alloy)
60°C, lh 54%
Br Br
Tsukinoki, T.; Kakinami, T.; Iida, Y.; Ueno, M.; Ueno, Y.; Mashimo, T.; Tsuzuki, H.; Tashiro, M. J. Chem. Sot. Chem. Commun., 1995, 209
H2 , [ W2(~&t’BU)6(@)2 1
no yield Barry, J.T.; Chisholm. M.H, .I. Chem. Sot. Chem. Comma, 1995, 1599
74 Compendium of Organic Synthetic Methods, Vo19 Section 74B
SECTION 74B: Formation of Aryls OMe
/
LiCl , CuBr , inhibitor Pd(PPh& , dioxane , reflux OMe
&.& J.M.; MartoreU, G. J. Org. Chetn., 1993, 58, 1963
bMe
Crrissom, J.W,; Calkins, T.L.; McMillen, H.A. J. Org. Chem., 1993, 58, 65%
50 at.m CO, AC@
PhooAc PdCl2W’bh 9 mt3
PhH , 140°C, 3h *
OAc 69%
Ishii, Y.; Gao, C.; Xu, W.-X.; Iwasaki, M.; Hidai. MJ. Org. Chem., 1993, 58, 6818
C
HSiMe$-Bu , C) (50 atm) Ru~(CO)~~/PCY~, 140°C, 20h
* *::::
45%
Chatani, N.; Fukumoto, Y.; Ida, T.; Murai. S, J, Am. Chem. SM., 1993, 11.5, 11614
%
PhOH , PhMe ,180”C
t 7h
0
Danheiser, R.L,; Gould, A.E.; de la Pradilla, R.F.; Helgason, A.L. J. Org. Chem., 19% 5%
5514
Section 74B Formation of Aryls 75
Sato, Y.; Nishimata, T.;
20% Ni(O)-PPh3 , HC=CH THF,23OC, 12h
N---Ts
91%
Mori. M, .I. Org. Chem., 1994, 59, 6133
PhCHO
1. PhNH2
2. Pd(OAc), , MeCN
;-;FHT3/ B
. 0 AQtZ
Rama Rao. AV,; Reddy, K.L.; Reddy, M.M. Tetrahedron Lett., 1994, 35, 5039 OH
I I
1.5 ~wipr)3 y
t
0.1 SnC14 , 0°C s
1.5 (MeO)$iMe3
78% -Si(iPr)3 Angle. SR,; Boyce, J.P. Tetrahedron Lett., 1994, 35, 6461
t-BuOOCOPh , Cu(OAc), CuBr , PhH , 80°C, 8.5h
56%
Tavares, F.; Mevers. A.1, Tetrahedron Lett., 1994, 35, 6803 N-OH
5% Pd/C , diethylene glycol
Bn 188OC , diethyl ether, 45 min Bn I
89%
Ar Ar = 4-methoxyphenyl Al-
Matsumoto. M.; Tomizuka, J.; Suzuki, M. Synth. Commun., 1994, 24, 1441
76 Compendium of Organic Synthetic Methods, Vol9 Section 74C
SECTION 74C: Alkylations and Arylations of Alkenes
2 BFjmOEt2 25OC
Maietich. G,; Zhang, Y.; Feltman, T.L. Tetrahedron L&t., 1993, 34,441
Maretich. G,; Zhang, Y.; Feltman, T.L.; Duncan Jr., S. Tetrahedron . Lett., 1993, 34, 445 Ar
Toluene , -45OC , 18h 2. LiEt3BH
3. MeOH 4. NaBH4
/OH
Ph
Ar = 2,6-di-t-Bu-4-OMephenyl 80% (84% ee)
Tomloka.; . Shindo, M.; Koga, K. Tetrahedron Lett., 1993, 34, 681
/ H
%
M N
0
+3-l”l
DMF , BuflCl , ld 10% Pd(OAc)z ,3 iPr2NEt
66:34 E.-Z, 99% Me NH2 5 HC02Na
Larock.; Ding, S. Tetrahedron Lett., 1993, 34, 979 cat. Pd(OAc);? , Ag2C@
w-4 1
C02Me DMF ,45OC, overnight
Wll 75%
OH
OH
&ff@. T, Tetrahedron L&t., 1993, 34, 1133
Section 74C Alkylation of Alkenes 77
1. Et&Cl Me
2. BuZnCl , DMF
* J==i
60%
OH Bu
5% C12Pd(PPh3)2 OH
2 BuLi ,5h . .
Nenlshl,; Ay, M.; Gulevich, Y.V.; Noda, Y. Tetrahedron Lett., 1993, 34, 1437
0 v
SnBu3
10h
Zhang, H-C.; Brakta, M.; Daves Jr,. G.D, Tetrahedron L&t., 1993, 34, 1571
OTf 0 0 , 30°C, 91h
58%
Pd(R-BINAP)2 , PhH Proton Sponge
87% ee, R C)zawa. F,; Kobatake, T.; wi. T, Tetrahedron Lett., 1993, 34, 2505
x
Pi0 SnBu3
Q-I 1 1I , AIBN , To1
46h, 85OC 52%
Kinnev. W.A, Tetrahedron Lett., 1993, 34, 2715
Bu$nmNI-12
PhBr , To1 ,2% Pd(PPh&
- phm,, 47%
R.J&; Geng, B.; &Iore;ill. J.JE J. Org. Chem., 1993, 58, 1443
w-h7 w-b3 00
H
1. Me2SCHC02Et Bu$n B(W l312 2. H202, NaOAc
Dem. M.-Z,; Li, N.-S.; Huanrr. Y.-Z,J. Org. Chem., 1993, 58, 1949 60%
Compendium of Organic Synthetic Methods, Vo19 Section 74C
Br
J&; Qabar, M.N. J. Org. Chem.,
0
1993, 58, 4473
OMe
1. PdC12 , LiCl , THF o”c + 25OC
2. aq. NH4Cl ] -PhINH2
Larock. R.C%; Ding, S. J. Org. Chem., 1993, 58, 2081
(CH2)8co2Me
/ /9-BBN
PhOTf , Pd(PPh3)4, 85OC
&PO4 , dioxane - ph- (cH2)&02Me 87%
2. PhHgCl , O2 0
60% (74:26 E:z)
Oh-e, T.; &G\raura. N.: Suzuki. A, J. Org. Chem., 1993, 58, 2201 Ph
Ph 1.2 Et$n , 1.5% PdC12(dppf), THF 1.2 Et$n , 1.5% PdC12(dppf), THF 2. CuCN.2 LiCl
2. CuCN.2 LiCl 3.
3. C02Et C02Et
Stadmiiller, H.; Lentz, R.; Tucker, C.E.; S tiidemann, T.; Diirner, W.; Knochel. J. Am. Chem.
Sot., 1993, 115, 7027
phi 3 eq. EtMgBr , Cp$rCl2
THF,rt,6h
Suzuki, N.; Kondakov, D.Y.; Takahashi, T, J. Am. Chem. Sot., 1993, 11.5, 8485
Section 74C Alkylation of Alkenes 79
N2+BFd C02Et
4 , EtOH
2% Pd(OAc)z , 60°C, lh
C02Et
71%
SenguPta.; Bhattacharyya, S. J. Chem. Sot., Perkin Trans. l., 1993, 1943
OH 5 eq. MeMgBr
0.05 PdC12(PPh3)2
OH
VW,; Giesen, V.; Fuest, M. Liebigs Ann. Chem., 1993, 629
e, , DMF , Et&104
Ni(teta)(ClO&
Ozaki. S,; Horiguchi, I.; Matsushita, H.; Ohmori, H. Tetrahedron Lett., 1994, 35, 725 97%
47%
iMe LDA, TMS-Cl
C3H
06 * C3H
THF , -78OC Et
Wright. S.W, Tetrahedron Lett., 1994, 35, 1841
Et 93%
02Me
Phi , Bu4NHS04, aq. MeOH 02Me
5% [Pd(OAc)2/2 PPh3] 96%
Heck reaction in aqueous media Jeffery. T, Tetrahedron Lett., 1994, 35, 3051
0 0
A Phi , SmIz/THF , 15 min
Ph DMSO A/ Ph 47%
0 Ph
Nazareno, M.A.; Rossi. R.A, Tetrahedron Lett., 1994, 35, 5185
Compendium of Organic Synthetic Methods, Vol9 Section 74C
Ph Pd(OAc)2, Bu3P, 3h IS2CO3 , DMF , 80°C
+ + Ph Phi
OOCNHMe
quant. (78 6)
Ono, IS.; Fugami, K.; Tanaka, S.; Tamaru. Y, Tetrahedron Lett., 1994, 35, 4133
I 0 2 AlEt , 0°C
SPh b
10h 0
Majetich. G,; Zhang, Y.; Liu, S. Tetrahedron Lett., 1994, 35,4887 0
4 I
0
SPh 70%
,SnBuj
Pd(PPh3)4, THF ,65OC, lh
66%
Matthews, D.P.; Waid, P.P.; Sabol. J.S.: McCarthy. J.R, Tetrahedron Lett., 1994, 35, 5177
SnBu3
B. D,; Cardamone, R be 9 l Guzzi, U. Tetrahedron TfO
OMe
OMe 70%
1.
SnBu3
/
5% Pd2(dba)3 ,20% AsPh3 w 2.5% TFA , CH2C12
= Rink amide resin 89%
Deshnande. M.S, Tetrahedron Lett., 1994, 35, 5613
Section 74C Alkylation of Alkenes 81
phwseMe 2 eq. MesSiCHzMgCl b
5% NiC12(PPh&, DME l?h-siMe3
reflux , 1.5h 79%
Hevesi. L,; Hermans, B.; Allard, C. Tetrahedron Left., 1994, 35, 6729 1.0.3 q3-C3HSPdC1)2 , HSiPh2F
Ph-
0.6 o’-diphenylphosphinobinaphthol derivative Ph
Me
20°C , 10h P
2. MeLi S iPh2Me
96% (66% ee, S) Hatanaka. Y,; Goda, K.; Yamashita, F.; Hiyama, T. Tetrahedron Left., 1994, 35, 7981
/
/‘Q 0 NH
NC NH2
Mn(OAc), , CuOAc ultrasound ,4h
47%
12
Bosman, C.; D’Annibale. A.; Resta, S.; Trorrolo. C, Tetrahedron Left., 1994, 35, 8049
0 OTf Bufl+ (Ph3SnF2)‘, THF
- 8-
Ph Pd(PPh3)4, reflux ,30 min
81%
A.&; Barcina, J.O.; Cerezo, A. de F.; Subramanian, L.R. Synlett, 1994, 1047
10% ZrC12(qC&), 1.5 BuMgCl II, 6h
Takahashi. T,; Kotora, M.; Kasai, K. J. Chem. Sot. Chem. Commun., 1994, 2693
1. BuLi , THF , -7OOC 2.ZnBr2, -7OOC + 2o”c
t 3. H30+
,SiUe3
81%
82 Compendium of Organic Synthetic Methods, Vol9 Section 74C
C$-I&Me#H , Et3SiH tridecane , di-t-Bu hyponitrite
t AcH$(H$)4\/ SW3
65%
Dang, H.-S.; Roberts,.P, Tetrahedron Lett., 1995, 36, 2875
Br*COOH
PhSnCl3, aq. KOH ,3% PdC12
* Ph*COOH 83%
Rai, R.; Aubrecht, K.B.; Collum. D.B. Tetrahedron Lett., 1995, 36, 3169
cylization-Diels-Alder Joumet, M.; B. m J. Org. Chem., 1995, 60, 6885
Chavan. S.P,; Ethiraj, KS. Tetrahedron Lett., 1995, 36, 2281
OMe OMe
BF3eOEt2, C&I 12, refk y 2h
56%
Maietich. G,; Liu, S.; Siesel, D. Tetrahedron Lett., 1995, 36, 4749
section 74C Alkylation of Alkenes 83
Ph 10% Pd(OAc)z ,20% Bu3P
Phi , DMF, 100°C, 1Sh
S.-K,; Jung, K.-Y.; Park, C.-H.; Namkoong, E.-Y.; Kim, T.-H. Tetrahedron Lett., 1995,
Zhang, W.; Dowd. P, Tetrahedron Lett., 1995, 36, 8539
95%
Yu, J.; Cho, H.S.; Falck. Tetrahedron Lett., 1995, 36, 8577 .
JEt3 , PhMe , reflux 5% RuH2(CO)(PPh&
94%
Trost.; Ixni, K.; Davies, I.W. J. Am. Chem. Sot., 1995, 117, 5371 1. Me3Al,8% Cl$ZrCpz , DCE ,22OC
y” 2.02
92% (74% ee) Kondakov, D.Y.; Negishi.J. Am. Chem. Sot., 1995, 117, 10771
84 Compendium of Organic Synthetic Methods, Vol9 Section 74D
OTf 4 CO,Et ,5% PdC12(PPh3)2
w 3 LiCl , DMF , 1 10°C Draper, T.L.; mv. T&SynZett, 1995, 157
0
%
Si(OEth
, toluene ,135OC Ru(H)2(CO)(PPh& 7 2d
c
S i(OEt)g 0
Kakiuchi, F.; Tanaka, Y.; Sato, T.; Chatani, N.; Murai. S, Chem. Lett., 50% 1995, 679
1. BC13 , CH2C12, O°C
ph-sMe3 2. catechol , PhH - PhwPh 86%
3. PhBr , Pd(PPh& , NaOH
Farinola, G.M.; Fiandanese, V.; Mazzone, L.; Naso. F, J. Chem. Sot. Chem. Commun., 1995, 2523
REVIEW:
“Recent Developments and New Perspectives In The Heck Reaction,” Cabri. W,; Candiani, T.
Accts. Chem. Res., 1995, 28, 2
SECTION 74D: Conjugate Reduction of a&Unsaturated Carbonyl Compounds and Nitriles
0 0
4
2% [Pd(Pt-Bu)(PHt-Bu&
02 9 H2 (10 psi)
I THFJ3h
) 4
90%
glass autoclave
Me Me
Sommovigo, M.; u.H.Tetrahedron Lett., 1993, 34, 59 OH
Eta- 9 ~&oh6
CO (1 atm) , NE@ ,3O”C
t ph/\/co2ph
80%
bh. x; Fujiwara, IS.; Takahashi, S. Bull. Chem. Sot. Jpn., 1993, 66, 978
Section 74D Conjugate Reduction 85
PhSiH3 , 20°C, 16h MO complex
(62 . . 38) 95% conversion Schmidt. T, Tetrahedron Lett., 1994, 35, 3513
Ph*CHO
NaHTe , EtOH rt ,5h
w phmCHO
>98%
Yamashita. M,; Tanaka, Y.; Arita, A.; Nishida, M. J. org. Chem., 1994, 59, 350 TFA-Et3SiH ,30 min
-78°C + O°C
various protonic and Lewis acids used zhao, Y.; m. P,; Keo, E.A. Tetrahedron Lett., 1994, 35, 4179
NH4+ HC02-, Pd-C 25OC ,4h
t
Ranu. B.C; Sarkar, A. Tetrahedron Lett., 1994, 35, 8649
phmNo2
Bakers yeast, 31°C
3d =, pheNo2
shl&, . M..; Yoshida, S.; Kohno, Y. Heterocycles, 1994, 37, 553
43%
o=
limonene , 10% Pd/C , reflux 0
- o=
0 quant.
von Holleben. M.L,; Zucolotto, M.; Zini, C.A.; Oliveira, E.R. Tetrahedron, 6994, 50, 973
86 Compendium of Organic Synthetic Methods, Vol9 Section 74E
PhA
Na&Od , aq. dioxane ,5O”C , lh
* Phi
ECHO ICI-IO
selective reduction of conjugated carbonyl C=C units
Dhillon. RS,; Singh, R.P.; Kaur, D. Tetrahedron L&t., 1995, 36, 1107 Sm , 12 , MeOH , 1 min
t ph/\/C02Et
97%
a; Bessho, K.; Yanada, K. Synlett, 1995, 443
C02Me
BER-CuS04 , MeOH, rt BER = borohydride exchange resin Sim, T.B.; Yoon. N.M,SynZett, 1995, 726
wC02Et
NaBHeBiC13,95% EtOH t
C02Me
94%
- CO2Et
Ren, P.-D.; Pan, S.-F.; Dong, T.-W.; Wu. S.-HJynth. Commun., 1995, 25, 3395 98%
0 0
Bakers yeast
,; Saitou, K.; Hida, K.; Ohno, A. Tetrahedron Asymmetry, 1995, 6, 2143 SECTION 74E: Conjugate Alkylations
Ranu. B.c; Saha, M.; Bhar, S. Tetrahedron L&t., 1993, 34, 1989
Section 74E Conjugate Alkylations
PhS-
87
0’ Li+
6
\
b CO2Me ‘t, 6 C02Me
EL
2
SPh + CH2C12
2d, -78OC
(15
Corey. E.J,; Houpis, I.N. Tetrahedron Lett., 1993, 34, 24k P
h 1. PhMgBr , CuBr*SMez
Tv 2.NBS,THF,-78°C *
0
Li, G.; Jarosinski, M.A.; J-In&y. V.J, Tetrahedron Lett., 1993, 34, 2565 0 PhguLi , THF , -78OC 20%
+ TMSCl 81%
+ TMSCN 83% -k
Ph
; James, B. Tetrahedron Lett., 1993, 34, 6689
3 eq. mSnBu3 0.05 (Bu$n)z 6 eq. PhSCH(OMe)z
0.3 M PhH , hv
(sunlamp) Me h OMe 69%
(8: 1 transxis) mk. G&; Kordik, C.P. Tetrahedron Lett., 1993, 34, 6875
ea I Me(Boc)NCHzSnBu$s-BuLi
TMEDA , CuCN , TI-IF 1
& NMeBoc 98%
er. m; Alexander, C.W. Synlett, 1993, 407
88 Compendium of Organic Synthetic Methods, Vo19 Section 74E
$ Et 9 Eu( tfc)3 Et
MS , Ccl,, -33OC, 72h
-* 71% (25%ee)
Eu(tfc)3 = [tris-(3-trifluoromethylhydroxymethylene)-d-camphorato] europium (III)
Bonadies, F.; Lattanzi, A.; Orelli, L.R.; Resci, S.; Screttri. Tetrahedron L&t., 1993, 34, 7649
1. BnOCH~CH+CH/Cp$Zr(H)Cl 2. MeLi , Me$u(CN)Liz
81%
rnshutz. R.H; Wood, M.R. J. Am. Chem. Sot., 1993, 115, 12625
1. Ni(aca&
2.
0
-w
-3
80%
Eshelby, J. J .; Crowley, P. J. ; Parsons. P.J,Synlett, 1993, 279
Bu - /-co2Et
1. Me2CuLieLiI
* 2. MeOTf
Amdt, S.; Handke, G.; Krause. N, Chem. Ber., 1993, 126, 251 SO2Ph 1. t-BuBr , Cr(en)2+2 , DMF ,4h t-Bu
\
4 - 2.H20 * \
S02Ph en = ethylene diamine
Tashtoush, H.I.; hstmann. R, Chem. Ber., 1993, 126, 1759
78%
Section 74E Conjugate AIkylations 89
Ph$b , cat. Pd(OAc);!
0 AgOAc , AcOH ,25OC Ph 0
41%
Cho, C.S.; Tanabe, K.; Uemura. Tetrahedron Lett., 1994, 35, 1275
3 eq. SmI2, THF ,-78°C
-E.J.; Trivellas, A. Tetrahedron Lett., 1994, 35, 1627 cat. Pd(OAc)z , NaOAc , Id cat. SbC13, AcOH ,25OC
* ‘“\(‘rf 88%
0 Ph 0
Cho, C.S.; Motofusa, S.; IJemura. S, Tetrahedron Lett., 1994, 35, 1739
r Me02
3 eq. Me$iSnBu3,2 eq. CsF DMF,rt, lh
Sate, H.; Isono, N.; Okamura, Br K.; Date, T.; Mori. M, Tetrahedron Lett., 1994, 35, 2035
MeTi(OiPr)dMgCl , TI-IF Ni(acac)z , -15OC + rt . 85%
Bs.; Kabbara, J.; Nickisch, K.; Neh, H.; Westermann, J. Tetrahedron Mt., 1994, 35, 6075
90 Compendium of Organic Synthetic Methods, Vo19 Section 74E
==c
t-BuHgCl , Et3SiH , DMSO
C02Et dark, hv (sunlamp) ) A
-35OC , llh Et$i C02Et
Russell. G.A,; Shi, B.Z. Tetrahedron Lett., 1994, 35, 3841 93%
Y
iPrCH0, LiNO3, aq. MeCN e’
C02Me +QL
34% 2
UT.; Soejima, T.; Takigawa, K.; Yamaguchi, Y.; Maekawa, H.; I(ashimura. S, Tetrahedron Lett., 1994, 35, 4161
,C02t-B u ::
1. BuLi, m =
C02teBu = t
-100°C + 3o”c
2. H-20 70% +
other isomers
Cooke Jr.. M.P,; Gopal, D. Tetrahedron Lett., 1994, 35, 2837
PhCHO , Ph2C0
hv 69%
Kraus. G.A,; Liu, P. Tetrahedron Lett., 1994, 35, 7723
MeMgCl , CeC13, THF
Bli. G,; Bosco, M.; Sambri, L.; Marcantoni, E. Tetrahedron Lett., 1994, 35, 8651
Section 74E Conjugate Alkylations 91
wey. a, Hajra, S.; Ghorai, M.K. Tetrahedron Lett., 1994, 35, 7837
Miura,
MeO&
Bu$nH , PhH
(1
Iondo, T.; Hosomi. A, Tetrahedron Le ‘tt.,
COzMe + . Wl $ 1) 54% W-I
1;94,35,9605
11
0 BuC=CH , PhC=CSnEtj , Me&Cl
%A Ni(acac)z , Dibal , THF , rt ,2h
80% (>95:5 E.-Z) Ikeda, S.; &to. Y, J. Am. Chem. Sot., 1994, 116, 5975
CHO
I 94% (93:7 1,4: 1,2) Kabbara. L; Flemming, S.; Nickisch, IS.; Neh, H.; Westermann, J. Synlett, 1994, 679
Et2Zn , MeCN , 1.5% NiC12 , -3OOC
phL ph 309’ chual pyrrolidine 0 l *Phuh
75% (82% ee , S) Asami. MJ Usui, K.; Higuchi, S.; Inoue, S. Chem. L&t., 1994, 297
92 Compendium of Organic Synthetic Methods, Vol9 Section 74E
Ph Z Li
Y CH2CI;!
I
99%
AI(OAr)3 , -78OC , lh
Ar = 2,5diphenylphenyl Ph
Maruoka, K.; Shimada, I.; Imoto, H.; Yamamoto. H, Synlett, 1994, 519 0
A
PhMezSi -N
HSiPhMe2 , toluene , 1 10°C
I [Rh2(oAc),l * dNJl
I
Bn Bn 87%
u T,; Oda, T.; Kimura, F.; Onishi, H.; Kanda, T.; I(;ito. S, J. Chem. Sm. Chem.
Commun., 1994,2143
ph&C02Me
1. PhMe#Li , Me$Zn , THF/toluene , O°C 2* aq* NH4C1
CO2Me 98%
73% using cuprate Crump, R.A.N.C.; wing.; Urch, C.J. .I. Chem. Sot., Perkin Trans. l., 1994, 701
5% CuBr , THF , TMSCl ,4h AlMe , 10% solution in hexane
96%
Kabbara. J,; Flemming, S.; Nickisch, K.; Neh, H.; Westermann, J. Chem. Ber., 1994, 127, 1489
t-Bu
t-Bu (t-Bu)2Cu(CN)Li2
w
C02Et
t-Bu
quant.
111111111
\ CO2Et Gerold, A.; .Krause. N, Chem. Ber., 1994, 127, 1547
Section 74E Conjugate Alkylations 93
C02Et
0
-A , DME ,0.3h LiOH , Hz0
. 96%
B FJ Forcellese, M.L.; Locati, L.; Screttri, A.; Scolamiero, C. Guzz. Chim. Ital., 1994, 124,467
-/c”u
PhBr , NiBr2, e’
63%
3 H20, DMF-Py , 80°C
* phwco2Et
Bumr , Bu&I
Condon-Guegnot- &; Leonel, E.; N&l&ec, J.-Y.; P&ichon, J. J. Org. Chem., 1995, 60, 7684 OSiMe3 0
5 M LiClOd , ether
Sarawathy, V.G.; Sankararaman.J. Org. Chem., 1995, 60, 5024 70%
t-BuZnBr , THF/pentane , -3OC 2 TMSCl , 1.5 BF3aEt2
Hanson, M.V.; Rieke, J. Am. Chem. Sot., 1995, I 17, 10775
iPr1, Bu$nH , Yb(OTf)3 t CH2Q/hexaneKHF . .
Slbl. M&; Jasperse, C.P.; Ji, J. J. Am. Chem. Sot., 1995, II7, 10779
Ph&
neat Al(C3H7)3 ,5% CuBr
76%
w; Flemming, S.; Nickisch, K.; Neh, H.; Westermnn, J. Tetrahedron, 1995, 51, 743
94 Compendium of Organic Synthetic Methods, Vo19 Section 74F
1. &D ,O”C,hv
2. LTA , PhH , heat
C02Me 98~25%
Barton, D.H.R.; Chem, C.-Y.; Jaszberenvi. JCs, Tetrahedron, 1995, 51, 1867
Wu, J.H.; Rad
61%(80%ee;10:90 R.-S) inov, R.; Porter. N.A, J. Am. Chem. Sot., 1995, 117, 11029
REVIEW:
“Intramolecular Michael and Anti-Michael Additions to Carbon-Carbon Triple Bonds,” Rudorf, W.-D.; Schwarz, R. Synlett, 1993, 341
SECTION 74F: Cyclopropanations, including Halocyclopropanations SO2Ph
‘CH(SOMe)2, DMSO
99%
20°C , 15 min
J-E,; Lofstom, C.; Juntunen, SK. Tetrahedron Lett., 1993, 34, 2007 N2CHC02t-Bu , CH2C12
-,P /,
CuOTF-biarylamine ligand P %, + ,,\+ \’ A *,
‘Cod-Bu ‘h %,
‘C02t-B u
(86 .
92% ee . 14) 75%
Ito, K.; Katsuki. T, Tetrahedron Lett., 1993, 34, 2661
C&I, CrCl$Fe 02Et
89%
C02Et Hu. C-M.; Chen, J. Tetrahedron Lett., 1993, 34, 5957
Section 74F Cyclopropanations 95
\ 70%
Kreif. A; Dubois, P. Tetrahedron Lett., 1993, 34, 2691
Ph
Bu$nN(Et)CO2Me, DCE
P
(93:7 1,2-tranxcis) Shibata, I; Mori, Y.; Yamasaki, H.; Baba, A.; Matsuda, H. Tetrahedron Lett., 1993, 34, 6567
P h
bis-Rh catalyst, styrene t 0
L4 h = = Ph Eo,?Me
+
63% 9O%ee Davies.; . Hutcheson, D.K. Tetrahedron Lett., 1993, 34, 7243
1. NBS, DMSO ,5 min
,,il/v/ ::::;:H * p
Kd’
H g2%
(>99: 1 cis: trans) Dechoux, L.; Ebel, M.; Jung, L.; Stembach. J.F, Tetrahedron Lett., 1993, 34, 7405
L”ToEt ) ; gg%
10% Pd(PPh3)4, DMF ,7h
0
Ogoshi, S.; Morimoto, T.; Nishio, K.; Ohe, K.; Murai. S, J. Org. Chem., 1993, 58, 9
96 Compendium of Organic Synthetic Methods, Vol9 Section 74F
(97 . . 3) 84%
avres. H.ML; Huby, N.J.S.; Cantrell Jr., W.R.; Olive, J.L. J. . Am. Chem, Sot., 1993, 115, 9468
Bu CHO
Montgomery, D.; Reynolds, K.;
CrC12 - DMF ,3h
32%
Stevenson. P,J. Chem. Sot. Chem. Commun., 1993, 363 SO2Ph
/
LiCH(SPh)S02Ph, THF
PhS I s c-
SPh -78OC + O°C t
81%
Bailey, P.L.; Hewkin, C.T.; Clegg, W.; kkson. R.F.W, J. Chem. Sot., Perkin Trans. I., 1993,577
Me I 0 - Na+ %H(C02Me)2, TI-IF-HMPA -70OC + O°C ,3h
Watanabe, Y .; Ueno, Y .; m. T, Bull. Chem. Sot. Jpn., 1993, 66, 2042 CH212, Zn , Et20
40°C, 8h Pb , Me$iCl
C@Me C02Me 63%
97%
SK.; Kakiuchi, T.; -0. Ic J. Org. Chem., 1994, 59, 2671
Section 74F Cyclopropanations 97
PhS,
Denis, R
b @Ylr::~~~: 302Me
Mac C02Me
.C.; Gravel. D, Tetrahedron Lett., 1994, 35, 4531
50%
0
- A_
/ +
NHSO&H,pNo,
Bu$n H OH
+ NHS02-C6H4p-NO2 86% ee (2S,3R), 94%
Imai, N.; Sakamoto, K.; Takahashi, H.; Kobavashi, S, Tetrahedron Lett., 1994, 35, 7045 (2 7 .
OH
ai
2 eq. Et@, CH&
CH$lz-hexane, -2OOC BGn,
%, + # H
1. PhCHN2 Ph
cp\ 2. PhCH=CHz , rt , 12h
OC-Fe-
oc / -4
80% (96:4 cixtrans) Ph Seitz, W.J.; Hossain. M.M, Tetrahedron Lett., 1994, 35, 7561
MezN &pNMe2
“)7 +
1. 0 \/ 0
B
PheOH
Bu w PhvOH
2.2.2 Zn(CH21)2
>95% (29: 1) Charette. A.B,; Juteau, H. J. Am. Chem, Sot., 1994, 116, 2651
Et$n , CH212, CH&
hexane , -2OOC
Ph-oH a
H s ,SO,Ph s :
a
N\ ,B-iBu N
H ‘SO Ph
Imai, N.; Takahashi, 11.; Kobayashi. S, Chem. Lett.,‘1994, 177
Ph
quant. (76% ee) OH
98 Compendium of Organic Synthetic Methods, Vo19 Section 74F
Ph Ph
’ @mSiMe Ph
Br Bu2Te 3
0 +
Ph
C&03, 7o”c DME , trace water
Me3Si . . MesSi 8) 93%
Y.-z; Tang, Y .; Zhou, Z.-L.; Xia, W.; Shi, L.-P. J. Chem. Sot., Perkin Trans. I ., 1994,893
3-pentanone/LDA , THF
* S02Ph
62%
Ericsson, A.M.; Plobeck, N.A.; mkvall. J.-E. Acta Chem. Stand. B., 1994, 48, 252
Zn ClMe2SiCH$H$iMe2Cl
Mo(.herwell. W.B,; Roberts, L.R. Tetrahedron L&t., 1995, 36, 1121 2 Ti(OiPr)d 4 iPrMgBr
-45OC + 0°C
Kasatkin, A.; Sate. Tetrahedron Lat., 1995, 36, 6079
PhaOH
Charette., Brochu, C. J. Am. Chem. Sot., 1995, 117, 11367
93% (58:42 trans:cis)
l.Zn(CH$)2
2. -78OC -+ -2OOC
3. TiQ * ph-YoH
90%
Section 75 Alkyls from Misc. 99
5% semi-corrin Cu complex , DCE 23OC
57% (95% ee) Pique, C.; Fahndrich, B.; pfaltz. A, Synlett, 1995, 49 1
1. XX12 , CC14, reflux 2. NaI04 , 0.1 RuC13
85%
3. Li 5% DTBB , THF
4. H20 Ar
Ar = 4- t-bu tylphen yl Guijarro, D.; Yus. w Tetrahedron, 1995, 51, 11445
REVIEW:
“The Asymmetric Cyclopropanantion of Acyclic Allylic Alcohols: Efficient S tereocontrol with Iodomethylzinc Reagents,” w. A&; Marcoux, J.-F. Synlett, 1995, 1197 SECTION 75: ALKYLS, METHYLENES AND ARYLS FROM
MISCELLANEOUS COMPOUNDS
~co2MhMe#-~-~~2~(OAc)~ LEMe
. 73%
as. Y,; Planchenault, D.; Weber, V. Tetrahedron Lett., 1994, 35, 9549
SOzt-Bu Ph
2 PhMgBr ,5% NiC12(PPh&
Clayden, J.; Cooney, J.J. A.; Julia. M c J. Chem. Sot., Perkin Trans. 1.) 1995, 7
77%
REVIEW:
“Organonickel Chemistry in Organic Synthesis. Some Applications of Alkyl and Metalacyclic Derivatives,” C&npora, J.; Paneque, M.; Poveda, M.L.; Carmona. E. Synlett, 1994,465
100 Compendium of Organic Synthetic Methods, Vol9 Section 77
CHAPTER 6