МСОС Лекции с поиском и закладками

2.1. PeaK4Mfl XeKa (-MM3opoK111)

Kpocc-COl.feTaHMe ra11oreHonpOM3BOAHblX C a11KeHaMM

1

R2

R

2

X= N2 > I > OTf > Br > Cl

1 :

R -X

-/Jlt

1

r

R Ar, HetAr, Vi, Bn

R2: H, Ar, COR, OR

Pd(O)/B

:

B NEt

KaTaI1MTM4eCKMM 4MKI1 peaK4MM XeKa

HBr BocCTaHOBl1Te/lbHOe

0

3/111MHHHPOBaH11e

r"'\...,.,.L

Q-a,

0

H-rd- Br

L,·6 \:''

A 0Kl1CJ111Te/1bHOe

np11coep,11HeH1-te

TT-KOMn/leKca

f.l-3/l11M11H11 -poeaH11e c

9

2.1. PeaKU,MA XeKa

• CKOpOCTb peat<U,IIIH XeKa H pereoce11eKTHBHOCTb C0'4eTaHlllfl a11KeHOB 3aBHCIIIT OT 3/leKTPOHHblX Ill npocrpaHCTBet,jHblX 3q,q,eKTOB 3aMeCTIIITe/leH

	Pd(OAc)2		(1 Mon. /o)
			0
-\ +	PPh3 (2 Mon. %)
	Br
		Et3N
				R	R

100%

i

-\COOCH3

100°/o

! -\ CN

100%	80%20%		60% 40%	100%
*	!	!	* i	!
-\	-\		-\	-\
Ph		C4Hg		OCH3

oJ)

•PeaKU,lllfl XeKa 11acro nporeKaer 8 >KeCTKHX VC/IOBHRX, ycKOpReTCfl PTC, Ag(I), Tl(III)

•BHHlll/lranareHHAbl coxpaHRIOT crepeOXHMIIIIO 8 peaKU,IIIH XeKa

0

0 0

-Br OMe

Bu' 'v' Pd(OAc):z/PPh3/K2C03 Bu OMe OMe

TEBAC/DMF/RT 90%

2.1. PeaKU,MJI XeKa

0	0

Br	OH HO						.o N
N Pd(OAc)2/PPh			/NEt3
H	DMF/RT						HO	Ph
N2BF4 Ph						Ph
							OEt
	Pd(OAc)2/	,,,......					______.. EtO
				.o		Pd(OAc)2/PPh3/TBAC
	EtOH/ so0c I						DMF/ ao0c	0

• AnR xnopnpo1113BOAHb1x 111cnonb3Vt0T Pd(O) c AOHOpHblMIII n111raHAaM111

0

-9'......,,, Cl ,J-o

Meo ::::,...	Pd2(dba)3/P(t-Bu)3	MeO ::::,.._
	Cs2C03iAHOKCaH/T

0

0KT"1HOKCaT

0

e

0

H

H

11

0

O

11,.,0H

0

1.

(COCl)2

O

N

N N

Me

,.,

CF3

C

11,.,0H

2. NH3

'

s

3. COCl2

a

2 3

H2/Pd/

I

s

N

0 O

,.

N

2

Pd (dba)

CF3

H2

N

Me

AcONa/AcOH

4.

ttI

YO

F3 npocynbcJ>ypoH

1

F3

NIN

2.1. PeaKU.MA XeKa

• Ap111n111poeaH111e rerepo4HKJ10B

I

Pd2(PPh3)4/Cul

Cs2C03/DMF/T 70%

!t BHyrp111MoneKynRpHble eap11taHTbl peaKl..\111111 XeKa np111MeHRIOT AnR ClltHTe3a Kap6o H rerepo4HK/IH'leCKHX CIIICTeM

NaOAc
TBAC/DMF/T	\
90%	Ac

	\			\N
	N
,:?	Br N	Pd(OAc)2 /PPh3	,:?
	N	NaHC03/TBAC/		N	0
	I	DMF/T		I
					80%

Cu cycle

2.2. PeaKU,Mfl CoHorawMpbl

Kpocc-co"leTaHHe ranoreHonpOM3BOAHblX C anKMHaMM 003BOJ1ReT cl,opMHpoeaTb
C-C CBR3M Me>KAY sp2 H sp aTOMaMM
			X= I > OTf > Br > Cl		KaTaI1HTlll4eCKHM '-'HKil
			R1 : Vi > Ar, HetAr
	Pd(O)/Cul/B		R2: Ar, COR
			B: NEt3
HO		HO
	TMS		TBAF		Pd cycle
	Br ------J►			►
			N'/ ·--= rMs MeCN
	Pd(PPh3)2Cl2/Cul/				TM
HO	NEt3fTHF

					HO
	OH			Br--< /J	0
'/			·>-
				___	O►Me
N			=

Pd(PPh3)2Cl2/Cul/

NEt3fTHF

	OH
N	'/	·>--==- ·

OH	OH

0

/J OMe

CuX	[Cu :=: R2 ln
SuX	LbaseHX
	/(base
H _,_	R2

OH

,,,,,.Q

Br

HO

NaH

,,,,,.Q

..

Pd/C/PPh3/Cul/

N

I

\

PhMe

N

I

\

1

K2C03/0ME

92.%

Anil!IHIIIKOl!IH

3.PeaKU,Mfl 6yxeanbAa - XapTBHra

0N

H

Bu	;;	Br Pd(OAc)zldppf Bu	;;			N
		t-BuONa/PhMe/
		120°C,48h
	-	H2N-Ph				Ph
Bu	;;	Cl Pd2(dba)3/X-PHOS Bu	;;			NH
		KOH/H20
		100°c,4ah

• Kpocc-co4eraH111e 6yxeanbAa-Xapre111ra ycnewHo np111MeHJ1ercJ1 AnR ct,opM111poeaH111J1 C-0,

C-S, C-P 1,1 C-C CBR3eH					,---,. ,d			0-
			Nao
								-
;;			r Pd2(dba)3/FcP(t-Bu)2
				tBuOK/H20
					120°c, 12h
								74%
								0
'-:::::							'-:::::
							I o
o		OH		Pd(OAc)2/PPh3
	Br			K2C03/PhMe/ T

1	90%

3. PeaKU,MJI 6yxeanbAa - XapTeMra

F

,._efOH bH

-

Br - I

MeO--<
Pd(PPh3)2Cl2/PPh3/
K2C03/DME0	- MeO

H2otso c

F.

tBuOK

/J

Br 89%

0

HS

OEt

Pd2(dba)3/0PEPHOS/

K2C03/PhMe-1120°c112 h

- -

85%

THFtso0c,a h

OEt

Meo s

94%

• Kpocc-COL4eTaHMe C eHOnM3VIO MMMCff npOM3BOAHblMM						MO>KeT 6b1Tb
111cnonb30BaHo AnR <l>opM111posaH111R C-C cBR3eH Me>KAY sp2 111 sp3 aroMaMM
H		EWG		0				0	Ph
Ar-X	R ..		ArxEWG			Ph-OTf
				?" -...,,,					,1111Me
						Pd2(dpa)3/
Pd(0)/8			R R
			X= OTf> I> Br		(R)-OIFLUORPHOS			81%
					t-BuONa/PhMe/T
			EWG: COR, CN, N02					ee=90%
1			8: t-BuONa

Pa3Aen V

MeTOAbl cpopM1t1posaH1t1fl C-C 1t1 C=C CBfl3e

3. MeTOAbl CHHTe3a anKeHOB

MeTOAbl CMHTe3a anKeHOB

1. rMAPMPOBaHMe anKMHOB

2.TpaHc<l>opMaU.MA anKeHOB (KpOCC-CO"leTaHMe M MeTaTe3MC)

3. PeaKU.MM 3nMMMHMpoeaHMA (OTU\enneHMe BOAbl Ill ranoreHOBOAOPOAa)

4.PeaKU.MM BMTTMra III XopHepa

5. KOHAeHcau.111111 allbAOllbHOroTMna

1.rMAPMPOBaHMe anKMHOB

BapbMPOBaHMe MeTOAa BOCCTaHOBJleHMR no3B011ReT nony aTb 4uc-,mpaHc-a11KeHbl (CM. MeTOAbl BOCCTaHOBJleHMR)

2. TpaHc4>opMal4MR anKeHOB

2.1 Kpocc-co1.1eraHMe (peaKU,MM XeKa, KyMaAa, Cy3yKM, Kop1i1-Xay3)

				Me2Culi
			>--OTf	THF ► -+-		Me
t-Bu
/THF			OEt			Ph
			Pd(PPh3)4		Pd(PPh3)4
		,__..,. I NEta			K2C03

1		- - - - -- --------·····	Et