Copper catalysed alkynylation of tertiary amines with CaC2 via sp3 C-H activation

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00872K, Communication

Siew Ping Teong, Dingyi Yu, Yin Ngai Sum, Yugen Zhang
A mild and easy-to-handle protocol to produce propargylamines with a terminal alkyne through sp³ C-H bond activation and C-C coupling of tertiary amines and calcium carbide has been developed.

Copper catalysed alkynylation of tertiary amines with CaC2 via sp3 C-H activation

Copper catalysed alkynylation of tertiary amines with CaC₂ via sp³ C–H activation

Siew Ping Teong,^a   Dingyi Yu,^a   Yin Ngai Sum^a and  Yugen Zhang*^a  

*Corresponding authors

^aInstitute of Bioengineering and Nanotechnology, 31 Biopolis Way, The Nanos, Singapore 138669, Singapore
E-mail: ygzhang@ibn.a-star.edu.sg

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00872K

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00872K?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

A mild and easy-to-handle protocol to produce propargylamines with a terminal alkyne through catalytic cross-coupling of tertiary amines and calcium carbide has been developed. The reaction proceeds via sp³ C–H bond activation and C–C coupling. Good to excellent yields were obtained for the corresponding propargylamines with both alkyl and aryl substitutions. The development of these functionalized propargylamines with a terminal alkyne group will offer a wider application for the synthesis of natural or pharmaceutical products due to their unique sp C–H reactivity.

N-methyl-N-(prop-2-yn-1-yl)cyclohexanamine (3a) This compound was prepared according to general procedure and isolated by column chromatography (ethyl acetate/hexane = 1/8) to give the product as a light yellow liquid (139 mg, 92%). 1H NMR (400 MHz, CDCl3) δ 3.42 (d, J = 2.4 Hz, 2H, CH2), 2.39 – 2.31 (m, 1H, CH), 2.35 (s, 3H, CH3), 2.19 (t, J = 2.5 Hz, 1H, C≡CH), 1.92 – 1.90 (m, 2H, CH2), 1.78 – 1.75 (m, 2H, CH2), 1.62 – 1.59 (m, 1H, CH2), 1.31 – 1.08 (m, 5H, CH2); 13C NMR (101 MHz, CDCl3) δ 79.8, 72.6, 60.7, 42.9, 38.5, 29.8, 26.0, 25.5; HRMS (EI) m/z calcd. for C 10 H 17 N 151.1361; found 151.1358

/////Copper catalysed alkynylation,  tertiary amines,  CaC2,  sp3 C-H activation





 Gokarna, India. karnataka

Gokarna, India

Town in India

Gokarna is a small temple town on the western coast of India in the Kumta taluk of Uttara Kannada district of the state of Karnataka. The main temple and deity is Lord Shiva, who is also known as Mahabhaleshwara. Wikipedia

 

 

 

HOW TO REACH GOKARNA

Gokarna is located in Karnataka just a few hours from Goa and Bangalore. Although it does not have an airport, it is well-connected by road to all major cities. Here is how to reach Gokarna.

By Air

Dabolim airport in Goa is the nearest airport about 140 km away. The airport is well connected by flights to Indian and international cities. From the airport, taxi services are available.

By Train

The nearest railway station is at Ankola, about 20 km from Gokarna. Trains from several cities including Mangalore, Mumbai, Thiruvananthapuram, Veraval halt at the station. From the station, taxi services are available for Gokarna.

By Road

Gokarna is well connected by road. KSRTC buses do ply regularly from Bengaluru, Mangalore, Hubli, other cities of Karnataka. One can also board a bus from Madgaon and other cities of Goa for Gokarna. Gokarna is just 10 km off the NH 17 connecting Mumbai to Kochi. Buses, including AC luxury, ply regularly between both the cities.

 

Paradise Beach, Gokarna.  Anders Blomqvist/Lonely Planet Images/Getty Images

By Sharell Cook

India Travel Expert

Updated March 28, 2016.

Gokarna is a small and remote holy town, with four of India's most secluded and pristine beaches nestled nearby. It draws both pious pilgrims and hedonistic holidaymakers with equal enthusiasm. Travel to Gokarna to get a feel for what Goa was like in its heyday, although time is limited as developers are already seeing the potential of this area and commercialization is setting in.

Location

Gokarna is located in the state of Karnataka, an hour south of the Goa border. It's around 450 kilometers (280 miles) from Bangalore, the state capital.

Getting There

The nearest airport is Dabolim, in Goa. From there it's a four hour drive south to Gorkana. Alternatively, trains on the Konkan railway stop at Gokarna Road station, 15 minutes from town, as well as Kumta and Ankola stations, both around 25 kilometers (16 miles) from Gokarna. Gokarna is also well connected by bus from major cities such as Madgaon in Goa, and Mangalore and Bangalore in Karnataka.

Climate and Weather

Gokarna experiences the southwest monsoon from June to August, following which the weather becomes dry and sunny. The best time to visit Gokarna is from October until March, when the weather is warm and pleasant with temperatures averaging 32 degrees Celsius (90 degrees Fahrenheit). April and May are hot summer months, and the temperature easily reaches 38 degrees Celsius (100 degrees Fahrenheit) then. It becomes very humid too.

What to Do

Gokarna's main attraction is its beaches, where people come to chill and soak up the sun for months at a time. As Gokarna is one of the most sacred holy towns for Hindus in south India, there are also some important temples to see. Unfortunately, they're off limits to non-Hindus but you can grab a glimpse inside. The Mahabaleshwar Temple houses a huge lingam (symbol) of Lord Shiva. Make sure you check out the huge chariots near the Ganpati Temple, which carry a Shiva idol through the streets while people throw bananas at it for good luck during the Shivaratri Festival in February/March.
In addition, it's possible to learn yoga (most classes are held on Kudle Beach) and to surf. Read More: 8 Top Places to Surf and Get Lessons in India.

Beaches

Gokarna town has its own (rather unclean) beach that's popular with pilgrims. However, the beaches that are of most interest to tourists are located one after another, a short distance away to the south. There are four of them -- Kudle Beach, Om Beach, Halfmoon Beach, and Paradise Beach (in that order). Each has its own appeal.
Om Beach is the most happening beach, and is the only one that's reachable by car or rickshaw.  However, this means that it attracts plenty of rowdy domestic tourists and locals, particularly on weekends, and unfortunately the men don't always behave themselves. Therefore, laid-back Kudle Beach is a preferable alternative for those who want to be around other travelers. This beach is situated in between Gokarna and Om beaches, and can be reached in 20 minutes from Om beach or by a short downhill walk from drop-off points. The other much smaller beaches -- Halfmoon and Paradise -- are to the south of Om beach. They're a scenic 30 minute hike away from each other through the hills and over rocks, or a short boat ride away. Paradise Beach, the last beach, isn't much more than a tiny protected cove that's a patch of hippie paradise.

Where to Stay

Gokarna town has plenty of hotels but they are characterless places. Instead, opt for a homestay such as Hari Priya Residency.
Better still, find yourself a hut on the beach. Decent ones are longer super cheap though, as many establishments have upgraded to concrete structures with attached bathrooms. Prices skyrocket from December to February, when demand is high, although it's much less costly than Goa!  Om and Kudle beaches both have some permanent accommodations, while places only open on Paradise and Halfmoon beaches during the tourist season from November to March. If you want to book in advance, try Paradise Holiday Cottages on Kudle Beach.
Nirvana Guest House is the best place to stay on Om Beach. Namaste Cafe is also popular. Beach accommodation can be difficult to come by in the peak months of December and January though. Many people are just happy with a hammock! If that idea doesn't appeal to you, make sure you turn up before noon to grab a room as people are checking out.
There are a few luxury resorts on the hillside, such as Om Beach Resort, SwaSwara, and Kudle Beach View Resort & Spa to cater for those who prefer their comforts. Om Beach Resort has a traditional Ayurvedic center, while Swaswara focuses on yoga and meditation.
For something different, check out Namaste Yoga Farm in the hills above Kudle Beach.
Alternatively, backpackers will be pleased to know that a Zostel hostel opened up in early 2016. It sits on a hilltop halfway between Gokarna town and Kudle Beach, and the beach view is rather spectacular. It's an arty place with dorms, private wooden cottages, a common room, and a yummy restaurant.

Parties and Nightlife

Bonfires, singing, guitars, and drums are familiar parts of Gokarna's nightlife. The party scene in holy Gokarna is kept in check by strict policing, although some beach parties do happen during the peak season. Officially, alcohol is banned because of the town's religious significance but you won't have a problem getting a cold beer on the beach.
 
 

Dangers and Annoyances

Police corruption has become a significant issue in recent years. After you arrive, your auto-rickshaw or taxi may take you to a police checkpoint, where your luggage will be searched for drugs (this includes prescription drugs) and hefty bribes extorted for possession. Also, do be aware that police are known to visit guest rooms and extort bribes from those found to be in possession of narcotics. Care should be taken when walking between the beaches at night in the dark, and it's best not to go alone. Swimming can also be dangerous as some areas have strong currents.

 


 
 

A Weekend for Me, Myself, and I in Gokarna Paradise

Posted on March 26, 2013 by amberbeserra

2

After constantly being around people for what seems like a few months now, I finally got the opportunity to head out on my own for the weekend! I made my way 3 hours north of Manipal by train to a little sandy paradise named Gokarna. I left Friday afternoon and didn’t return until Monday evening, and I loved every minute of it.



The train ride there was extremely easy and even quite. I had an entire section of a car just to myself. I arrived at the station in Gokarna just as the sun was setting, so I grabbed a taxi for the 20 minute drive from the station to where I was staying. To get there, the taxi had to go on dirt backroads full of potholes, but it was well worth the bumpy ride. I splurged a little and decided to stay at a yoga farm on a cliff overlooking one of the beaches. And because it is the end of the season, they gave me a cottage all to myself for a discounted price.

Roommate 1

Roommate 2

Roommate 3

When I got there Friday night I dropped my stuff off and headed straight for the beach. From the yoga farm, it is a 5 minute walk down the road to get to Kudle beach (there are 5 beaches in Gokarna, and Kudle is one of the best for tourists besides Om beach). I soon found myself sitting at one of the shacks along the beach having seafood noodles and a cold beer and enjoying the moonlight over the Arabian sea. I walked around the beach for a bit before heading back to my cottage to sleep.

Trail from the yoga farm to the beach

Included with my accommodations, I got to do yoga there every morning then have a delicious breakfast. The farm was started by a German couple who then hired on an Italian yoga instructor. They come over to India from October until April to run the farm and relax every year. And better yet, they live in tree houses. That is a serious childhood dream come true!

Treehouses!

Before yoga, we would sit around the community area and have warm ginger-lemon-honey drinks and get to know each other. There were only 3 other guests there from Austria, Britain, and Holland. The yoga was great – we practiced for 1.5 hours each morning on the yoga deck in the jungle. All the time, we could hear the waves crashing below and monkeys were swinging in the trees around us. Then after yoga we went back to the community area and got breakfast. Each morning I got fruit salad with museli and curd and then toast with a fried egg, real cheese (SO HAPPY), and tomato. What a great way to start my day!

Yoga deck in the jungle

Community area

After that, both on Saturday and Sunday I headed down to the beach. Both of those days looked just like this: swim in the ocean, lay in the sun, grab a fresh fruit juice, trek over the cliffs from Kudle beach to Om beach, swim in the ocean, lay in the sun, grab a snack, trek back over the cliffs, swim in the ocean, grab dinner, sit on the beach and watch the sunset, hang out with new friends on the beach, sleep. The ocean was so warm and the waves weren’t too harsh so sometimes I stayed in the water for over an hour until my fingers were prunes. Kudle beach is a bit smaller than Om and  really only has tourists while Om beach (which is shaped as an Om) is larger and has more locals there. To get from one beach to the other is about a 30 minute hike up and then back down the cliffs.

Om Beach. The picture is taken from the top of the Om.

Trekking from one beach to the other.

Kudle Beach. Across the way up on the hill in the jungle is the yoga farm.

My favorite beach shack – Namaste Rock Cafe

Mint milkshake made with real mint. Delicious.

Because it was near to the end of the season and many vendors are closing down and leaving back home, most those that were still there were very friendly. They would sit down with me on the beach and we would start talking. Very few of them actually tried to sell me anything. On Saturday night when I was watching the sunset, a young girl (15 years old) and her brother (6 years) came and sat with me. They are normally from Hampi, but come live with their aunt in Gokarna during tourist season to sell jewelry on the beach to make money to send home. The girl kept commenting on how pretty I was because I was white and how much she didn’t like that she was dark. She called me ice-cream and herself monkey. It was really hard to hear a young girl being racist against herself, although it is very common throughout India that darker skin is not as highly looked upon as lighter skin. Soon their aunt came and sat with us. And when I told her that I was studying to become a doctor all three of them shook my hand before she pulled out a piece of paper. It was the report from a recent ultrasound that she had gotten because she has had stomach pain for two years. She asked me to look at it for her, and even though I tried to tell her that I wasn’t yet a doctor she still wanted me to look. Her doctor had told her to take some pills, but that they had not been helping. The report said that her appendix was inflamed, but that all other abdominal organs were okay. I really wish I could have helped her, but without training it wasn’t ethical for me to recommend anything. So the only advice I could give her was to listen to her doctor. I am here in India to study public health, yet when Im away from my studies I got the most eye-opening experience related to it.


Before they left, I did want to get a few necklaces from them. They had already given me a black necklace, which they said was to remind me of them because they are dark, and an Amber colored bracelet to match my ring. When I went to pay, I didn’t have any small change. They told me to take the two necklaces I had picked out and to just pay them tomorrow. The amount of trust is incredible! I did find them the next day and brought them some cold water and paid them. Altogether a real eye-opening and touching interaction.

Also, because Gokarna is a popular stop for single travelers making their way through India, I met a number of friends from different areas. On Saturday, I had dinner with a girl from Britain, Amy, and a guy from Brazil, Filipe, who had run into each other traveling. Amy left early Sunday morning to continue with her travels, but Filipe stayed another day and we enjoyed each others’ company for the rest of the weekend. He is also a medical student in Brazil, taking a year off to travel the world. It was really interesting comparing aspects of my life in America and his in Brazil since we are on such a similar path. On Sunday night we went out with a guy from Britain who was staying at the yoga farm and is taking a year to travel. After a few beers we all ended up in a drum circle around a fire on the beach with people from India, Sweden, Chile, and more that I don’t even know. I absolutely loved it- complete strangers from such different areas with different ideas can wind up in the same place and have an amazing time together.
On Monday morning, after my yoga and food routine, Filipe and I walked into town before heading to the train station. To get to town, you have to walk across a cliff which is bare, dusty, and hot. You feel like you are wandering through a desert, until you can look out and see the beaches and ocean.


After a short walk through town and quick glimpse of the temples, we had to make our way to the train station 20 minutes away to make sure we could get train tickets. We got there 2.5 hours early and ended up just hanging at the station reading, talking, and listening to music until the train came.


The train was incredibly crowded, so we were forced to stand for the first little bit until others left their seats. We were also the only tourists in the car. But I made it back to Udupi and then Manipal via auto rickshaw safely and very happily.
It was such an amazing weekend- not only was it gorgeous scenery, delicious food and drink, fun swimming and trekking, and really good yoga practice, but I had amazing company. It didn’t matter if I was just with myself or with some of my new worldly friends, I was having an incredible time. I got to know myself better and I learned new things (such as how the British like to party and some about Buddhism and the process of becoming a doctor in Brazil and much more). This is definitely a weekend I will not be forgetting!
And to make things even better, on Thursday my dearest mother is coming to visit! She is landing in Mumbai/Bombay where I will meet her. We will spend the weekend exploring the city before taking a train back to Manipal where I will show her around my new stomping grounds.

https://amberbeserra.wordpress.com/2013/03/26/a-weekend-for-me-myself-and-i-in-gokarna-paradise/

 

 read............http://thrillingtravel.in/2015/08/10-things-to-do-in-gokarna.html

On Gokarna beach the children and I had good spontaneous fun etching circles in the sand and creating mandalas within them.

Our sand circles

Mandalas in the sand

Jeremy and George on the beach

Two beaches to the south, passing through the very hippy Kudle beach, one can climb up over the headland to reach Om beach on the other side. The beach is named Om due to its shape being like the sacred omkara, the only beach like this in India. 

Traveller crowd at Om beach

Cows enjoying Om beach

Making friends with some visitors from Dandeli

We met some young men on holiday, who were from the village of Dandeli. There was Kushol, the playful one, Ishmael whose car they'd come in but who slept most of the time, Manu who was enchanted by Rosina, Uvee who flirted with a young German girl nearby, and the boss of a paper factory called Pomy who flirted with me, and even said he was in love with me.

Kudle beach, not having a road leading to it like Om,was the best really for the hippy crowd to do their thing with few spectators. 

Calf suckling from its mother on the beach

Visiting a Russian Yoga Centre, which overlooks Kudle beach, I found myself in the midst of a Lakshmi puja fire ceremony, especially to celebrate the New Year, a good time to honour the Goddess. A handsome Indian holy man called Shiva Swami performed the ceremony, surrounded by beautiful, delightful Russian girls who were very into the Hindu way. Shiva Swami spoke of Lakshmi, she who cares about both our material and spiritual welfare, and blesses us with good qualities such as love and compassion, a beautiful smile and a happy heart. 

Shiva Swami performs a Lakshmi puja

The fire yagna began with worship of the elephant god, Ganesh, as all yagna's must do to be effective. Lots of mantras were chanted by Shiva Swami with accompanying 'Swaha's' chanted by everyone. Holy oils were poured on the sacred fire. I joined in chanting the mantra's, the mantra to Lakshmi being 'Om krim ha Lakshmi namaha'.
We focused on the flames, imagining good things for the world and for ourselves, and chanted a special mantra for the divine union of Shiva and Shakti, a mantra that is used in the temples of Ammaji the hugging guru, 'Om Shiva Shakti kyeru pinyay namaha...... swaha'...
There was also a special Goddess mantra, the Shakti Peeth, chanted by all Hindu's during the nine days of Navaratri, 'Om ayeem krim klim chamundayee vijay....... swaha'.... The sacred word 'ayeem' is the bhij mantra of Saraswati and brings one to wisdom. The sacred word 'krim' is the bhij mantra of Lakshmi and brings emotional purification. The sacred word 'klim' is the bhij mantra of Kali and brings power. The word 'chamundayee' illustrates that ones whole existence is Shakti Ma. This mantra is a good potent mantra, which protects one from all kinds of vengeance and brings about a highly powerful spiritual awakening.
Shiva Swami told us that there was so much energy in this yagna that it would protect us forever and ever. 

Coconut water from the coconut stall

Cow of Gokarna

Fruit delivery

Spring water from the mouth of a cow

The Rama temple which overlooks the sea has good spring water to drink. This flows from the stone head of a cow, around which are little naga snake deities. This mineral water, its is claimed, will cure illnesses. 

The Rama temple halfway up the cliff overlooking Gokarna

View from the cliff of Gokarna beach

Cave where Shiva was born from the ear of a cow

Up above Kudle beach is the cave where Shiva emerged from the ear of the cow. A small shrine is in its dark depths and many bats. The smell is stifling though, hard to breathe in there.  On the cliff near there, overlooking the sea, is the spot where Garuda, the divine bird of the Ramayana, came crashing down when slain by Ravana.

Yoga is practised as cold drinks arrive in Kudle beach

Georgie enjoying the sea

One of the hippy characters of Gokarna, Guy of France

Hippy Guy from the Auvergne, with his impressive pink motorbike. Guy was connected with a cultish group in Kerala, where, as he told me, the inner core members have some strange habits, living naked, and sharing one another sexually. They even send their children away not to be brought up by either parent.

Roman who bought an auto-rickshaw

Roman in his rickshaw

An English guy, Roman, had become the proid owner of an auto rickshaw, which both impressed and amused me, for this he now intended to travel around India in, his first destination being Hampi. 

Friend of the monkeys

Adi lingam, the original lingam of the Shiva temple in Gokarna, surrounded by water

Steps down to the adi lingam

Resident frogs at the sacred yoni - at the shrine of the Adi Lingam

Though the inner shrine of the great Shiva temple is closed to foreigners we were welcome to look around the rest of the temple. Down some steps we went into the shrine of the Adi lingam, which was the original lingam long before the one in the inner shrine
It was set in a pool of water in which frogs swam, and was a special place of worship. 
Foreigners were also allowed into the Parvati shrine, the shrine of Shiva's bride. Once a year Shiva is brought to her here to enact a marriage ceremony. 

A crow was plucking hairs out from the cows tail

Brahmani kite which represents the divine god Garuda

Pretty blue bird

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