МСОС Лекции с поиском и закладками

4.1. BoccraHoeneHMe rMAPMAaMM 6opa

2.3. ACCMMeTpMl.feCKMe 6opaHbl: lpc2BH, anbnMH6opaH, CBS-OKCa3a6oponMAMH

• 2-MeTMn... CBS-0Kca3a6oponMAMH (R,S-} AllR crepeoceneKTHBHoro KaTanHTH\tecKoro BOCCTaHOBneHMff KeTOHOB (BOCCTaHOBneHHe no MtcyHo-KopH HnM KopM...6aKWM-WM6ata)

0 1. 2PhMgBr

OMe 2.TFA

OH

R

0H

Ph

Ph

-B1,

Ph

------►►

Q-i-

BH3

►

\....§{

h

Ph

~N

OH

'

.,...O

-=N

0

B

B.,...

H.§}ef

I

/

'H

I

R

R=H (S)-0KcaJa6opo111,1A1,1H;

H

R=Me (S -2-Me-CB5-0KcaJa6opon1,1.q1,1H;

Ph

(S)-2-Me-CBS

Ph'f,..½)

t

,

o, ,,7

HO H

0

0

11111

II

►

,.

X

/',..

(e-

8 10

I I H

CF

RL H-'-B-

(a-) Rs

1. F,C

<t:, > Cl

0

I

(S)-2-Me-

CBS

►

N/

NaH/OMF

I

-

N/

BH3"THF

H

I

e 2.HCI

<l>ny0Kcen1H

Bo

*HCI

4.2. BoccTaHOBneHHe rHAPMAaMH antoMHHHff

1. AntoMOrMAPMA JlMTM (LAH) LiAIH4 - BbtcoKoaKTMBHbtM soccraHOBMTenb <1>YHKU,MM

•BOCCTaHOBneHMe KMCnOT, 3<1>MPOB, 300KCMAOB, Kap60HMnbHblX COeAMHeHMM B cnMpTbt;

•HMTpMnbt, aMMAbl, OKCMMbl, HMTpoanKaHbl, HMTpoanKeHbl B aMMHbl (KpOMe ArN02);

CJ:

R

OH

O

----►

-("'H

g:;:

s

-{

s

ns

ns

:r

H

:r

R

0

0

m

al

OR'

s

-

---•►

R

OH

a.

s

s

Q.

-(,,,H

L..

s

c:(

C{

s

H

L..

s

l­

1-

o

OH

(,)

0

►

R-(,,, .

0

0

Q.

0

la::

:ii::

0

H

R

(,)

R

OH

►

\

l,,,

H

H'''T""°\

H

R'

MexaHM3M BOCCTaHoeneHMff -nepeHocrMAPMA·MOHa

Li

@

H18

o

l'o

oL·1

\

R'

NR'

LiAIH4

R

)1

---.-,

_/

AIH3

10-AI-H

\@

R-f

2

)1111

/\

()

HI

-- 0N

'

NR

NR 2

H

'2

R

'2

H

H-AI-H

H N

H

81

H0-AI1 -H

H

H

R'

- ►

R'\N-R'

R_/H

\

H

4.2. BoccTaHoeneHMe rMAPMAaMH a/ltOMHHHff

1. AntoMorHAPHA nHTHR (LAH) LiAIH4

• nponaprHn0Bble cnHpTbl B E-annH/lbHble cnHpTbl

HeA0CT3TlO1 LAH: nMppo<l>opHOCTb, repMH ecKaR HeCTa6H/lbHOCTb, HH3K3ff paCTB0PHM0CTb B paCTB0PMTe/lRX,TPYAH0CTH BblAeneHHR np0AYKT0B

2. AnaH AIH3 - 6011ee aKTHBHblH eoccraH0BHTenb, eM LAH

3LiAIH4 + AICl3

.., 3AIH3 + 3LiCI

• B0CCTaHoeneHHe <l>YHKU.H0Ha/lbHblX rpynn (KpOMe HHTpo- H anKeHOB)

0

0

4.2. BoccTaHoeneHHe rHAPHAaMH antoMHHHR

3. AHH306yrH11a11toMOrHAPHA (DIBAL) HAl(i-Bu)2

• CtepM\feCKM 3aTPYAHeHHblM MffrKMM BOCCTaHOBMTe/lb, npMMeHRIOT AJlff

BOCCTaHOB/leHMff npOM3BOAHblX Kap60HOBblX KMC/10T B a/lbAerMAbl
	HAl(i-Bu)i	R	___@		·'sI		R	iBu	H2O _/JO		r
R =N :	►			N	t{	H1Bu	► )=N-A(_		► R\
			'-.J:Y				H	1Bu	H
0
d0	HAl(i-Bu)2								H
	-1a0c ►
									OH

AHanorM\fHO:

O

R· /J R-1(

bR' Cl

0

HO

0

OH

NaNO

2

1)-<0

_H_C_I_►►. 0 o OH

BH

3

*S

Me2

•

.		HAl(i-Bu)i
		-
O O		PhMe
	OH -7aoc

	I\. -
HO	An/\
	O OH

• rMApoantoMMHMpoeaHMe anKMHOB

4.2. BoccTaHOBneHHe rHAPHAaMM antOMHHHff

4. AAKOKCHrHAPHAbl a/llOMHHHff

4.3. BINAL-H (R,S)

• BOCCTaHOBMTenb AnR CTepeoceneKTMBHOro BOCCTaHoeneHMR KeTOHOB

00/H

O"''Al@ 'OMe

Li

(RJ-BINAL-H

fl {RJ-BINAL-H

►

0	(R)-BINAL-H
II	THF	►
Ph
		ee =95%

00.,H		1. BINOL
o"''AlOMe			LiAIH4
	MeOH
Lff>

	0
(R)-BINAL-H	► A111HonpocToH
►	---•► (PGE2)
	►

4.2. BoccTaHOBneHMe rMAPMAaMH antOMHHMff

4. AnKOKCMrMAPMAbl a11t0MMHMSf
4.1. llHTMSf rp1i1(mpem-6yroKcH)at0MorMAPMA (LTBA)
LiAIH4	LiAIH(Ot-Buh

• MRrKHH BOCCT3HOBHTenb AJIR BOCCTaHOBneHHR xnopaHrHAPHAOB M 3KTHBMp083HHblX
3<l>HPOB Kap6oHOBblX KHCnOT B anbAerMAbl					0
O		O	O	LTBA
	LTBA
Ph-{	THf' Ph	-{		v---c:
		H
OPh	_78oc				80%

4.2. HaTpMR 6MC (MeTOKCM3TOKCM)alOMOrMAPHA (SMEH, RedAI}

• BblCOKOaKTHBHblX BOCCTaHOBMTenb AJlff <l>YHKL\MOHanbHblX rpynn, TepMM"ieCKH

CTa6MnbHblH M paCTBOpMMblM B opraHH4eCKMX pacrsopHTenRX

R -

1

/OH1.SM 2.H0

R OH

[O]

(AE)

•

OH

R : OH

/

0

L\

R -, -OH

	OH
1.SMEH
----►► R	OH
2.H®

5. BoccTaHOB/leHMe paCTBOPRIOIJ..\IAMHCR MeTannaMIA

5.1. W.eno4Hble MeTannbl B cpeAe A0H0poe np0T0H0B

MexaHH3M BOCCT3HOBneHHJI CBJ13aH C nepeHOCOM 3neKTPOH MeTanna K cy6cTpa-ry. PeaKL\Hff Ha"tHHaeTCJI KaK OAH03/leKTP nepeHOC (SE71 C o6pa30BaHHeM aHHOH paAHKana

O6pa30BaHHe Ken1Aa - HHAH­ KaTop a6conton1poaaHHfl p-neu

Kervin 6eH3ocpeHoHa

• Na/EtOH(BuOH) .. Hcno11b3Vt0T Anff eoccraHoeneHMff Kap6oHHnbHblX 34>HPHblX rpynn, reTpOL\HKnoe (MeTOA 6yeo-6naHa)

0 Na OH

EtOH

0Na

►		OH
OEt EtOH
	flaypHnOBblH cnHpT

Na...

BuOH

5. BoccTaHOBneHMe paCTBOpfftOW,MMMCff MeTannaMM

5.1. UJ.en0'4Hble Merannbl B cpeAe AOHOBOB npOTOHOB

• Ao6aeKa NaNH2 6noKHpyeT eocCTaHoeneHMe TepMMHanbHblX

H

• Na/NH3/EtOH npMMeHRIOT AJlff conpff)f(eHH0ro B0CCTaH0BneHMe a,'3-HenpeAenbHblX

KeT0H0B C 803M0>KH0CTblO anKMnHpoeaHMff eH0/lffTa B a-nono)f(eHMe

H H

NaO
	o- H	mpaHc-H

R

• Na(Li)/NH3/Et0H -

5. BoccraHOBneHMe paCTBOpfftOIJ.\MMMCff MeTannaMM

5.1. Lll.eno Hble MeTannbl e cpeAe AOHOBOB npOTOHOB

eoccraHaenMeaeT 6eH30HAHYto apoMaTMKY AO 1,4-

U.MKnoreKCaAHeHoe (MeTOA 6ep1.4a). 3neKTpOHHble 3cP<l>eKTbl BnMSltoT Ha peaynbTaT M
cKopoCTb peaKU.MM (3A CHM>t<ator, 3A yaenHl.fMBatOT cKopocTb)
0 ONa	•	0	ONa •	O	OH
			0	1.H
				►
				SET
3A	SET			23..H(±)

OMe	OMe	•
U Na/NH3/EtOSET H		e
-------►

1.H►	OMe H20	o
(±)
2. SET U	TFA	cr

3.H

3A

OMe

OMe

3A

0

Na/NH 'EtOH

3 ►

5. BoccTaHoeneHMe paCTBOpfftOIJ.\HMHCff MeTannaMM

5.2. nepeXOAHble MeTannbl e cpeAe KMCnoT (Zn, Fe, Sn/H+ )

• Zn-Hg /HCI - npMMeHs:uoT AJlfl eoccTaHoeneHMfl KeToHoe no MeTOAY KneMeHceHa (a/lbTepHaTMBa MeTOA KM>KHepa-Bonbcl>a)

R C=O

H• H,O•

R-C-R

Zn (Ho)
;;//
Zn'l? A
?
t>	.,.

	Zn-Hg/HCI..
0	(1.NH2NH2
	2. KOH/DEG/T)
XonecTaHOH	XonecTaH

• Zn(nbl/lb) /H+ (AcOH, HCI) - npMMeHRIOT AJIR AeranoreHMPOBaHMR (Br, I)

00

s

				Br		Br
	CCl4	Br	s	Br	!:::. ...
						0
	3Br2				Zn/AcOH
		►
						s